Optimization of P3CPenT-Based Hole Transport Layers to Boost Efficiency in Perovskite Solar Cells

Optimization of P3CPenT-Based Hole Transport Layers to Boost Efficiency in Perovskite Solar Cells | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Optimization of P3CPenT-Based Hole Transport Layers to Boost Efficiency in Perovskite Solar Cells Nida Fatima, Khuram Ali This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7659823/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Organic and perovskite solar cells have fascinated world because of their excellent charge carrier mobility, ease of fabrication and high power conversion efficiency. This study has focused on the molecular design of hole-transporting materials (HTMs) using P3CPenT as a reference molecule for perovskite solar cells. Newly designed small molecules are evaluated using DFT with different functionals (WB97XD, CAM-B3LYP, PBEPBE, MPW1PW91 and B3LYP) with basis set 6-311G (d,p) in GaussView 6.0 and Gaussian 09W. Key properties such as absorption spectra, HOMO-LUMO energy gaps and excitation energies are analyzed. Molecular optimization and energy gap graphs are generated using Origin 6.0. These results have highlighted the potential of these molecules as HTMs with promising implications for enhancing solar cell performance. Physical sciences/Chemistry Physical sciences/Energy science and technology Physical sciences/Materials science Physical sciences/Physics Density functional theory (DFT) Perovskites Thiophene Optimization Optoelectronic properties Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 1. Introduction Concerns about pollution, resource depletion and securing sustainable energy sources have been heightened by the notable increase in global energy consumption, driven by industrialization and population growth in developing countries[ 1 , 2 , 3 ]. Recent advancements in organic solar cells (OSCs) which have achieved over 18% efficiency can be attributed to improved active layer materials, optimized interfaces and enhanced bulk-heterojunction film morphology[ 4 , 5 ]. Organic solar cells[ 6 , 7 , 8 ] utilize conductive organic polymers to transfer charges and absorb light. To ensure stability, they require encapsulation, morphological control and interfacial engineering. When produced using roll-to-roll methods, they are cost-effective and can be paired with lithium-ion batteries to enhance performance. Achieving high power conversion efficiency hinges on donor and acceptor materials with high extinction coefficients, well-aligned energy levels, nanoscale phase separation and high charge carrier mobility[ 9 , 10 ]. Perovskite solar cells (PSCs)[ 11 , 12 ] have achieved an efficiency increase from around 10% to over 22% since 2012, surpassing other technologies. However, challenges with stability, scalability and environmental impact still persist[ 13 ]. Perovskites have led to the growth of perovskite solar cells were discovered in 1839. These cells initially had an efficiency of 3.81% in 2009 and have now achieved 25%-29% efficiency. They utilize ABX 3 crystal structures with hybrid organic-inorganic compounds[ 14 ]. Perovskite solar cells are cost-effective, flexible and have adjustable energy gaps[ 15 , 16 ]. They also demonstrate strong light absorption and high charge carrier mobility. However, they are hindered by lead toxicity, material brittleness and production challenges[ 17 ]. Ongoing research is focused on enhancing their feasibility and addressing these issues. Modern high-performance perovskite solar cells (PSCs) use transparent conductive oxides and metals for the anode and cathode. The active layer produces photo-induced holes and electrons guiding the holes to the hole-transport layer and electrons to the electron-transport layer. Charge-transport layers like PTAA[ 18 , 19 ] increase the growth and stability of the cells[ 20 ]. To optimize perovskite solar cells, it is crucial to sensibly select and fabricate the three material layers, taking into account the layer thickness and carrier concentration. Research suggests that reducing the thickness of the hole-transport layer (HTL) and electron-transport layer (ETL) can help achieve sufficient coverage of the perovskite layer while meeting the carrier concentration requirements. The ideal absorber layer thickness ("absideal") in perovskite solar cells balances photon absorption with carrier generation and precise estimation is necessary for attaining optimal device performance[ 21 ]. An ideal HTM for perovskite solar cells needs to have compatible energy levels, high stability and mobility. It should also be solution-processable for scalability, affordability, and ease of preparation. Although Spiro-OMeTAD[ 22 , 23 ] is widely used, it often requires additives such as Li-TFSI and tBP. Alternatives such as PEDOT:PSS and P3HT are also being designed[ 24 ]. Scientists are developing hole-transporting materials (HTMs) using conductive polymers and inorganic semiconductors. However, issues with long-term performance and stability persist. Small molecule hybrid HTMs are increasingly preferred due to their availability, design flexibility and improved performance in solar cells[ 25 ]. A hole-transporting material is crucial for facilitating electron transport in perovskite solar cells. Despite being commonly used, Spiro-OMeTAD has limitations because of its low charge carrier mobility and high cost[ 26 ]. The presence of moisture in PSC induces the decay of MAPbI 3 into MAI and PbI 2 which contributes to environmental instability of PSC[ 27 ]. MAI is unstable and decomposes into CH 3 NH 2 and HI. When UV light and O 2 react with HI, it leads to significant degradation of the MAPbI 3 perovskite. Moisture-resistant HTL and ETL layers can protect MAPbI 3 , in addition to performing their charge transfer function. An organic ETL, F16CuPc, has been proposed for use in PSCs due to its moisture stability[ 28 ]. P3CPenT naturally forms nanowires when dissolved in DMSO, a solvent commonly used in PSC fabrication[ 29 ]. Kenneth et al. conducted a research on optoelectronic properties of P3CPenT. They discovered that using P3CPenT as a hole transport layer in organic solar cells can lead to an efficiency of 2.6%. Additionally, mechanical properties of P3CPenT films were assessed which highlighted their suitability for use in adaptable devices[ 30 ]. In this study, three organic donor compounds were designed connected with the reference molecule P3CPenT which were named as P3CPenT-1, P3CPenT-2 and P3CPenT-3. Reference and its designed molecules are executed using density functional theory (DFT) calculations. Each compound features a different acceptor group attached after the core (thiophene) of the molecule. Compared to the reference molecule (P3CPenT), these newly designed donor structures demonstrated notable charge mobility, a reduced band gap and enhanced absorption properties. We explored various photovoltaic structures to assess the photovoltaic properties of P3CPenT-1, P3CPenT-2 and P3CPenT-3 through extensive computational analysis. These donor compounds show significant potential to broaden the absorption spectrum. The thiophene spacers in these structures play a key role in promoting efficient charge transfer from the central core to the acceptor molecules. The designed molecules (P3CPenT-1 to P3CPenT-3) are likely to exceed the efficiency of the reference molecule, making them promising candidates to use as active layers in organic and perovskite solar cells. 2. Computational Approach Density functional theory is commonly used in computational quantum mechanical investigations[ 31 ]. In this study, geometric calculations for all molecules were performed using Gaussian 09 software then generated and visualized their 3D molecular structures with GaussView 6.0 software[ 32 ]. Density Functional Theory (DFT)[ 33 , 34 ] was used and five input files for the reference molecule R (P3CPenT) were created using five different functionals named as MPW1PW91[ 35 ], B3LYP[ 36 ], WB97XD[ 37 ], PBEPBE[ 38 ] and CAM-B3LYP[ 39 ]. This was done in order to optimize its structure and to minimize the risk of spin contamination in the results, basis set of 6-311G (d,p) and a restricted spin configuration was employed for the calculations. After optimizing the geometry, time-dependent self-consistent field calculations were conducted to obtain absorption spectra of the reference P3CPenT molecule in both gaseous and solvent state. The maximum absorption wavelengths (λ max ) were compared from five different functionals (Fig. 2 ) and found that the PBEPBE functional had a calculated λ max of 371.33 nm which was closest to the experimental λ max of 390 nm. As a result, PBEPBE was selected as the most suitable functional with a basis set of 6-311G (d,p). The absorption spectra for P3CPenT and P3CPenT-1 to P3CPenT-3 molecules were made using Origin 6.0 software[ 40 ] to analyze their ultraviolet-visible (UV-Vis) properties[ 41 ]. TD-SCF calculations were conducted using a preferred hybrid functional to predict the excited-state electronic behavior of molecules. The influence of the solvent (DMSO) on the maximum absorption wavelength (λ max ) was analyzed using the polarizable continuum model (PCM)[ 42 ] with the integral equation formalism (IEFPCM)[ 43 ] as the computational approach. Additionally, the functional PBEPBE with level of theory 6-311G (d,p) was employed to analyze the density of states (DOS), frontier molecular orbitals (FMOs)[ 44 ] and transition density matrix (TDM)[ 45 ] in addition to conducting geometry optimization. This functional was also used to calculate oscillator strengths, dipole moments, ground-state energies, excited-state energies and electron transfer effects for the reference P3CPenT and designed P3CPenT-1 to P3CPenT-3 molecules. Multiwfn 3.8[ 46 ] software was used to analyze the transition density matrix (TDM) which provided insights into the relocation of electron density between the excited and ground states of the molecules. Additionally, density of states (DOS)[ 47 , 48 ] plots were created using PyMOlyze 1.1[ 49 ] to visually represent the molecular orbitals and their energy levels. These analyses helped us gain a great understanding of transitions and the electronic structure in the reference P3CPenT and P3CPenT-1 to P3CPenT-3 molecules. 3. Results and Discussions 3.1 Optimized Geometries The geometries of reference and designed structures were optimized using the PBEPBE functional as shown in Fig. 3 . The key factors for understanding charge transfer and self-aggregation properties are conjugation and planarity within the designed molecules which are enabled through the optimized geometries[ 50 ]. The central core adopted an out-of-plane position during the optimization process to reduce the potential energy of the acceptor (Cyano-based, Methoxy-based and Pyridine-based) groups, thiophene spacers and surface P3CPenT donors. Thiophene serves as a π-bridge and exhibits exceptional optoelectronic properties and high hole mobility, making it an attractive choice for designing advanced hole-transporting materials[ 51 ]. Acceptors are frequently employed to optimize energy levels and analyze photovoltaic performance. For every molecule, bond lengths and bond angles were computed. In particular, Table 1 displays the bond length (d1) and dihedral angle (θ1) between the P3CPenT donor and the bridge, and bond length (d2) and dihedral angle (θ2) between bridge and the acceptor groups. The bond lengths (d1 and d2) range from 1.507 Å to 1.417 Å suggesting the presence of double bonds and conjugation via π-electron delocalization. Furthermore, all molecules (P3CPenT-1, P3CPenT-2 and P3CPenT-3) had θ2 values ranging from 179.19 to -179.52 degrees indicating negligible steric restriction to the freedom of rotation of the acceptor units. Table 1 Determined bond lengths and dihedral angles for the reference molecule P3CPenT and its modified structures P3CPenT-1, P3CPenT-2, and P3CPenT-3 Molecules d1 (Å) d2 (Å) θ1 (deg) θ2 (deg) P3CPenT 1.456 1.507 138.47 105.05 P3CPenT(1) 1.439 1.422 160.12 179.12 P3CPenT(2) 1.438 1.426 168.51 179.19 P3CPenT(3) 1.438 1.417 167.98 -179.52 3.2 Electronic properties Frontier molecular orbitals (FMOs) consist of the lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) and they play vital role to understand the electronic distribution in perovskite solar cells (PSCs). The HOMO located on the donor side resembles a valence band while the LUMO typically found on the acceptor side acts like a conduction band. The energy gap between LUMO and HOMO also known as band gap (Eg) is inversely related to molecular reactivity. Molecules with smaller band gaps tend to be softer, less stable and exhibit faster charge transport. The photovoltaic performance of perovskite solar cells is significantly influenced by LUMO and HOMO levels. In graphical representations, negative and positive phases of these orbitals are depicted by green and red colors, respectively. The investigation of FMOs revealed that electron density was transferred across the entire structure in all designed compounds. A wider spatial distribution of HOMO and LUMO resulted in enhanced optical absorption. For P3CPenT at functional PBEPBE and basis set 6-311G (d,p) level, the ELUMO and EHOMO values were calculated as -2.0517 and − 5.0499 eV, respectively. The designed compounds P3CPenT-1, P3CPenT-2 and P3CPenT-3 showed EHOMO of -5.3264, -5.1718 and − 5.19367 eV, and ELUMO of -3.9361, -3.6814 and − 3.9549 eV with corresponding band gaps of 1.3903, 1.4904 and 1.2388 eV. In all molecules, HOMO density was mainly localized on the core (donor) while LUMO density was distributed across both the core and acceptor signifying effective intramolecular charge transfer. Table 2 Estimated Eg values of the designed molecules at PBEPBE with 6-311G (d, p) level Molecule HOMO (eV) LUMO (eV) Energy gap (eV) P3CPenT -5.0499 -2.0517 2.9982 P3CPenT-1 -5.3264 -3.9361 1.3903 P3CPenT-2 -5.1718 -3.6814 1.4904 P3CPenT-3 -5.19367 -3.9549 1.2388 3.3 Optical Properties The absorption spectrum is a significant tool for analyzing the optoelectronic properties of molecules. When a hole transport layer (HTL) absorbs radiation equal to its band gap energy, it transitions to an excited state. Critical parameters such as excitation energy (Ex), dipole moment (µ), oscillator strength (f) and maximum absorption (λ max ) are assessed to understand how these molecules utilize solar energy for efficient charge transfer. A molecule with high f, strong absorption at a higher molar absorption coefficient (ε) and low Ex is expected to exhibit significant intramolecular charge transfer (ICT). The following table displays the observed absorption profiles of compounds: Table 3 λ max , Ex, f, µ g and LHE of reference and designed molecules studied in gaseous state Molecule Calculated λ max (nm) Excitation energies Ex (eV) Oscillator strength (f) Dipole moment µ g (debye) LHE (1–10 − f ) P3CPenT 369.84 3.3524 0.1912 1.335575 0.3561 P3CPenT-1 551.07 2.2499 0.7457 3.581910 0.8204 P3CPenT-2 539.51 2.2981 0.8985 3.231796 0.8737 P3CPenT-3 620.20 1.9991 0.8732 8.879381 0.8661 Table 4 λ max , Ex, f, µ g and LHE of reference and designed molecules with DMSO solvent Molecule Calculated λ max (nm) Excitation energies Ex (eV) Oscillator strength (f) Dipole moment µ g (debye) LHE (1–10 − f ) P3CPenT 371.33 3.3389 0.3426 1.847061 0.5456 P3CPenT-1 833.23 1.4880 0.8851 5.106566 0.8697 P3CPenT-2 803.98 1.5421 0.6368 5.111522 0.7692 P3CPenT-3 922.78 1.3436 0.8062 13.457676 0.8438 The oscillator strength (f) is an important optical property of molecules, directly linked to the energy gap (Eg). The absorption spectrum was analyzed using PBEPBE with 6-311G (d,p) level of theory calculations. This analysis revealed that the efficiency of perovskite solar cells depends heavily on absorption characteristics. In the gaseous phase, the molecules P3CPenT, P3CPenT-1, P3CPenT-2 and P3CPenT-3 demonstrated the strongest configurations at PBEPBE with 6-311G (d,p) level. The molar absorption coefficient for the reference molecule P3CPenT was determined using various functionals along with the basis set of 6-311G (d,p). Since wavelength and energy gap are inversely correlated, a higher energy gap is expected to result in decreased charge carrier mobility and lower oscillator frequencies. The findings showed that P3CPenT-1 has a higher frequency and is significantly red-shifted than the reference P3CPenT. These specially created compounds showed an absorbance spectrum from 369.84 to 620.20 nm. The predicted P3CPenT wavelength was 369.84 nm but the projected compounds P3CPenT, P3CPenT-1, P3CPenT-2 and P3CPenT-3 had gaseous phase wavelengths of 369.84, 551.07, 539.51 and 620.20 nm respectively. 3.4 Density of States (DOS) Density of states gives us a picture at different energy levels of electronic states and it highlights the contributions from HOMO and LUMO across various excited states. This research is important for understanding how charges move, as it shows us where there are a lot of electronic states available for charge carriers in the energy spectrum. DOS calculations for P3CPenT and some newly designed molecules (P3CPenT-1, P3CPenT-2 and P3CPenT-3) were conducted using the functional PBEPBE with a basis set of 6-311G (d,p) level. In the DOS of P3CPenT, contributions from acceptor, core and donor can be seen indicated by red, green and blue lines respectively, with total DOS (TDOS) represented by a black line. The HOMO peaks are observed between − 5.0499 to -5.3264 eV while the LUMO peaks appear between − 2.0517 to -3.9549 eV. The region without peaks between the HOMO and LUMO levels represents the energy gap (Eg). 3.5 Molecular Electrostatic Potential (MEP) MEP is significant for understanding how electric charges are distributed within a molecule and how they move. In polymer solar cells (PSCs), the MEP is crucial for processes like charge transport, separation and recombination, which all affect the efficiency of solar cells. This study examines the MEP of P3CPenT and its derivatives (P3CPenT-1, P3CPenT-2 and P3CPenT-3) to analyze how charges are spread out. The MEP helps to identify areas with an excess of electrons and areas lacking electrons within the molecule, showing where the molecule is most reactive. MEP maps use a color gradient, ranging from dark blue (positive potential) to red (very negative potential), to visually represent these areas. The electrostatic maps shown in Fig. 7 illustrate the three-dimensional distribution of charges within the molecules. The core of the P3CPenT molecule is depicted in a yellowish color while the designed molecules exhibit a blue tint around the core indicating the presence of acceptor units. This blue color shows that the acceptor units have the ability to attract electrons. Additionally, the color gradient on the maps represents electronegativity with red indicating areas of high electronegativity. The presence of red areas around P3CPenT-1, P3CPenT-2 and P3CPenT-3 indicates an increase in electron density around the acceptor units which contain electronegative elements such as nitrogen and oxygen. 3.6 Transition Density Matrix (TDM) It is important to analyze holes in matter in order to understand processes such as separation, diffusion and charge excitation. In this study, the charge transfer matrix, hole-electron distribution and transition density matrix (TDM) were simulated to explore charge transfer mechanisms in designed hole transport materials (HTMs). Heat maps of TDM and charge transfer matrix provided insights into the interactions between acceptor and donor core moieties during excitation. The mapping of hole-electron distribution revealed spatial overlap and contributions from both holes and electrons with the TDM maps indicating higher contributions from TPA groups and substituted acceptors. The designed HTMs demonstrated excellent charge transfer coherence and consistent charge generation while low coupling and increased charge separation suggested favorable conditions for efficient charge transport. 3.7 Analyzed Parameters V oc is the maximum voltage attained when there is no external current flowing. One can determine V oc using equation given as follows: V oc = (|E HOMO of donor - E LUMO of acceptor|)/e − 0.3 where V oc represents the maximum voltage output when no current flows through the circuit and a factor of 0.3 is introduced as a practical adjustment to account for real-world conditions. Furthermore, it is assumed that the generated molecules in this computational study work have a standard charge of 1 (so e = 1). The fill factor (FF) is a crucial performance parameter with theoretical values generally exceeding those obtained experimentally. It is determined using the following equation: $$\:FF\:=\frac{\frac{eVoc\:}{{K}_{B}\:T}\:-\:ln(\frac{e{V}_{oc}}{{K}_{B}T}+0.72)}{\frac{eVoc\:}{{K}_{B}\:\text{T}}+1}$$ In Table 5 , the values of J sc, V oc and FF can be found where the values were obtainedby using PC 61 BM as the acceptor and our studied compounds as donors. P3CPenT is expected to have HOMO and LUMO values of -5.0499 and − 2.0517 eV respectively. By using the LUMO of the PC 61 BM acceptor, the V oc values based on the HOMO values of our proposed molecules were estimated. Js c was calculated to be 21.3117 as reported in the reference literature and we compared our created molecules to this value. This comparison helps us to assess the impact on power conversion efficiency (PCE) of the specified molecules. PCE and J SC are directly related. The newly designed molecules P3CPenT-1 and P3CPenT-3 demonstrate a higher open-circuit voltage (V oc ) than the original P3CPenT molecule. This improvement in voltage generation is significant and is attributed to a greater shift in their LUMO energy levels. The PCE of the designed molecules is determined by the fill factor (FF) of designed molecules. The key factors influencing PSC performance such as electrical characteristics like short-circuit current density J sc , open circuit voltage (V oc ), normalized V oc , fill factor (FF) and power conversion efficiency (PCE)% can be used to derive this value which has no dimensions. Table 5 Optimized photovoltaic performances of the P3CPenT Molecule J sc (mA/cm 2 ) V oc (eV) Normalized V oc FF FF% PCE% P3CPenT 21.3117 1.0499 63.7643 0.9202 92.02 20.5896 P3CPenT-1 21.3117 1.3264 51.2618 0.9053 90.53 25.5909 P3CPenT-2 21.3117 1.1718 45.2870 0.8957 89.57 22.3683 P3CPenT-3 21.3117 1.1937 46.1333 0.8972 89.72 22.8246 Conclusion The P3CPenT-based hole transport materials (HTMs) and their derivatives have proven to be highly promising candidates for use in perovskite solar cells. Among these, P3CPenT-1 achieved remarkable power conversion efficiency (PCE) of 25.59%, significantly outperforming the widely used Spiro-OMeTAD (~ 20–21%) under comparable conditions. This enhanced performance was attributed to its optimized open-circuit voltage (V oc = 1.3264 eV), high fill factor (FF = 90.53%) and reduced energy gap (1.3903 eV) which collectively ensure improved charge transport and minimized energy losses. The alignment of LUMO level of P3CPenT-1 (-3.9361 eV) with the conduction band of perovskite absorber facilitated proficient electron blocking while its HOMO level (-5.3264 eV) supported effective hole extraction. Additionally, P3CPenT derivatives exhibited superior thermal stability, chemical durability and cost-effective synthesis compared to conventional HTMs like Spiro-OMeTAD. These findings highlighted the potential of P3CPenT-based HTMs as stable, efficient and scalable alternatives for advancing next-generation photovoltaic technologies, offering a sustainable path toward high-performance solar energy conversion. Declarations Funding This research was funded by the Higher Education Commission (HEC) of Pakistan [Grant No: 8615/Punjab/NRPU/R&D/HEC/2017]. Author Contribution N.F. conceived and designed the study, collected and managed the data, performed the analysis and interpretation, and drafted the manuscript. K.A. (corresponding author, [email protected] ) supervised the project and provided critical feedback and revisions. The final manuscript was reviewed and approved by both authors. Acknowledgement This work was supported by the Higher Education Commission (HEC) of Pakistan [Grant No: 8615/Punjab/NRPU/R&D/HEC/2017]. The authors also would like to acknowledge Prof. Khurshid Ayub, Comsats University Islamabad, Abbottabad Campus, Pakistan. Data Availability The datasets analysed and generated during the current study, including DFT output files and processed data are available in the Zenodo repository, [https://doi.org/10.5281/zenodo.17331313](https:/doi.org/10.5281/zenodo.17331313) . 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1","display":"","copyAsset":false,"role":"figure","size":336826,"visible":true,"origin":"","legend":"\u003cp\u003eλ\u003csub\u003emax\u003c/sub\u003e of the reference P3CPenT \u003cstrong\u003ea)\u003c/strong\u003e without solvent \u003cstrong\u003eb)\u003c/strong\u003e with solvent (DMSO)\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-7659823/v1/1c84eaf5bb0b9e2620ae2911.png"},{"id":94647080,"identity":"47e1bc20-8a2e-45fc-883f-bbadfc2df332","added_by":"auto","created_at":"2025-10-29 08:59:38","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":105204,"visible":true,"origin":"","legend":"\u003cp\u003eAnalysis of Calculated vs. Experimental λ\u003csub\u003emax\u003c/sub\u003e of P3CPenT across five different DFT functionals in DMSO 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HTMs\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-7659823/v1/a3eeb31f031f603c1655d091.png"},{"id":94672065,"identity":"a2796988-807c-442f-89e3-102b761b8012","added_by":"auto","created_at":"2025-10-29 13:38:11","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":256419,"visible":true,"origin":"","legend":"\u003cp\u003eFMOs for the reference molecule P3CPenT were calculated using PBEPBE functional with 6-311G (d,p) basis set, along with all designed molecules.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-7659823/v1/e80449f81c055fbae202ea9e.png"},{"id":94647092,"identity":"3d90d247-1988-42b1-9cd1-3ad88ab0b414","added_by":"auto","created_at":"2025-10-29 08:59:38","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":322443,"visible":true,"origin":"","legend":"\u003cp\u003eDensity of States around LUMO and HOMO of newly designed P3CPenT-based molecules using PBEPBE with basis set 6-311G (d,p)\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-7659823/v1/2b79c5080c69f6125bf62b9d.png"},{"id":94672649,"identity":"1493004d-6dc7-49ad-a78e-d5554761485c","added_by":"auto","created_at":"2025-10-29 13:40:48","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":854255,"visible":true,"origin":"","legend":"\u003cp\u003eMEP images of P3CPenT and P3CPenT-1, P3CPenT-2 and P3CPenT-3 designed molecules\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-7659823/v1/4429000f75f2ee0eb3a91e95.png"},{"id":94647087,"identity":"215cf19e-6e3e-4542-a468-88f9417e036f","added_by":"auto","created_at":"2025-10-29 08:59:38","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":798034,"visible":true,"origin":"","legend":"\u003cp\u003eElectronic transitions in P3CPenT-based molecules analyzed via TDM plots illustrating donor-acceptor interactions and charge separation\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-7659823/v1/74d223a39f943f8649010941.png"},{"id":94672274,"identity":"abe5c7b4-8c87-458e-9a76-cfea31b48071","added_by":"auto","created_at":"2025-10-29 13:40:06","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":190996,"visible":true,"origin":"","legend":"\u003cp\u003eCalculated V\u003csub\u003eoc\u003c/sub\u003e of P3CPenT and its Designed Molecules\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-7659823/v1/102be36ff3c84fb005d3dbf1.png"},{"id":95714097,"identity":"6ea8dbef-ee69-4ff8-81e3-44c47a3cf7ee","added_by":"auto","created_at":"2025-11-12 08:24:43","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4243082,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7659823/v1/538f5aa1-047a-4bc5-917d-83a9f4de398f.pdf"},{"id":94647117,"identity":"4828b1c4-234d-4ea9-96c7-909163c99bba","added_by":"auto","created_at":"2025-10-29 08:59:42","extension":"rar","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":91730333,"visible":true,"origin":"","legend":"","description":"","filename":"RawData.rar","url":"https://assets-eu.researchsquare.com/files/rs-7659823/v1/0bef0c959131cac4a3c81a96.rar"},{"id":94672721,"identity":"1952d8ef-6c74-4156-aeba-87763ce62f15","added_by":"auto","created_at":"2025-10-29 13:40:52","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":591132,"visible":true,"origin":"","legend":"\u003cp\u003eGraphical abstract\u003c/p\u003e","description":"","filename":"Graphicalabstract.png","url":"https://assets-eu.researchsquare.com/files/rs-7659823/v1/0dfc878d6de4dd6468d84354.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"Optimization of P3CPenT-Based Hole Transport Layers to Boost Efficiency in Perovskite Solar Cells","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eConcerns about pollution, resource depletion and securing sustainable energy sources have been heightened by the notable increase in global energy consumption, driven by industrialization and population growth in developing countries[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e, \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. Recent advancements in organic solar cells (OSCs) which have achieved over 18% efficiency can be attributed to improved active layer materials, optimized interfaces and enhanced bulk-heterojunction film morphology[\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e, \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. Organic solar cells[\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e] utilize conductive organic polymers to transfer charges and absorb light. To ensure stability, they require encapsulation, morphological control and interfacial engineering. When produced using roll-to-roll methods, they are cost-effective and can be paired with lithium-ion batteries to enhance performance. Achieving high power conversion efficiency hinges on donor and acceptor materials with high extinction coefficients, well-aligned energy levels, nanoscale phase separation and high charge carrier mobility[\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. Perovskite solar cells (PSCs)[\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e] have achieved an efficiency increase from around 10% to over 22% since 2012, surpassing other technologies. However, challenges with stability, scalability and environmental impact still persist[\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. Perovskites have led to the growth of perovskite solar cells were discovered in 1839. These cells initially had an efficiency of 3.81% in 2009 and have now achieved 25%-29% efficiency. They utilize ABX\u003csub\u003e3\u003c/sub\u003e crystal structures with hybrid organic-inorganic compounds[\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. Perovskite solar cells are cost-effective, flexible and have adjustable energy gaps[\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. They also demonstrate strong light absorption and high charge carrier mobility. However, they are hindered by lead toxicity, material brittleness and production challenges[\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. Ongoing research is focused on enhancing their feasibility and addressing these issues.\u003c/p\u003e\u003cp\u003eModern high-performance perovskite solar cells (PSCs) use transparent conductive oxides and metals for the anode and cathode. The active layer produces photo-induced holes and electrons guiding the holes to the hole-transport layer and electrons to the electron-transport layer. Charge-transport layers like PTAA[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e] increase the growth and stability of the cells[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. To optimize perovskite solar cells, it is crucial to sensibly select and fabricate the three material layers, taking into account the layer thickness and carrier concentration. Research suggests that reducing the thickness of the hole-transport layer (HTL) and electron-transport layer (ETL) can help achieve sufficient coverage of the perovskite layer while meeting the carrier concentration requirements. The ideal absorber layer thickness (\"absideal\") in perovskite solar cells balances photon absorption with carrier generation and precise estimation is necessary for attaining optimal device performance[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eAn ideal HTM for perovskite solar cells needs to have compatible energy levels, high stability and mobility. It should also be solution-processable for scalability, affordability, and ease of preparation. Although Spiro-OMeTAD[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e] is widely used, it often requires additives such as Li-TFSI and tBP. Alternatives such as PEDOT:PSS and P3HT are also being designed[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. Scientists are developing hole-transporting materials (HTMs) using conductive polymers and inorganic semiconductors. However, issues with long-term performance and stability persist. Small molecule hybrid HTMs are increasingly preferred due to their availability, design flexibility and improved performance in solar cells[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. A hole-transporting material is crucial for facilitating electron transport in perovskite solar cells. Despite being commonly used, Spiro-OMeTAD has limitations because of its low charge carrier mobility and high cost[\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eThe presence of moisture in PSC induces the decay of MAPbI\u003csub\u003e3\u003c/sub\u003e into MAI and PbI\u003csub\u003e2\u003c/sub\u003e which contributes to environmental instability of PSC[\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. MAI is unstable and decomposes into CH\u003csub\u003e3\u003c/sub\u003eNH\u003csub\u003e2\u003c/sub\u003e and HI. When UV light and O\u003csub\u003e2\u003c/sub\u003e react with HI, it leads to significant degradation of the MAPbI\u003csub\u003e3\u003c/sub\u003e perovskite. Moisture-resistant HTL and ETL layers can protect MAPbI\u003csub\u003e3\u003c/sub\u003e, in addition to performing their charge transfer function. An organic ETL, F16CuPc, has been proposed for use in PSCs due to its moisture stability[\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. P3CPenT naturally forms nanowires when dissolved in DMSO, a solvent commonly used in PSC fabrication[\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. Kenneth \u003cem\u003eet al.\u003c/em\u003e conducted a research on optoelectronic properties of P3CPenT. They discovered that using P3CPenT as a hole transport layer in organic solar cells can lead to an efficiency of 2.6%. Additionally, mechanical properties of P3CPenT films were assessed which highlighted their suitability for use in adaptable devices[\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eIn this study, three organic donor compounds were designed connected with the reference molecule P3CPenT which were named as P3CPenT-1, P3CPenT-2 and P3CPenT-3. Reference and its designed molecules are executed using density functional theory (DFT) calculations. Each compound features a different acceptor group attached after the core (thiophene) of the molecule. Compared to the reference molecule (P3CPenT), these newly designed donor structures demonstrated notable charge mobility, a reduced band gap and enhanced absorption properties. We explored various photovoltaic structures to assess the photovoltaic properties of P3CPenT-1, P3CPenT-2 and P3CPenT-3 through extensive computational analysis. These donor compounds show significant potential to broaden the absorption spectrum. The thiophene spacers in these structures play a key role in promoting efficient charge transfer from the central core to the acceptor molecules. The designed molecules (P3CPenT-1 to P3CPenT-3) are likely to exceed the efficiency of the reference molecule, making them promising candidates to use as active layers in organic and perovskite solar cells.\u003c/p\u003e"},{"header":"2. Computational Approach","content":"\u003cp\u003eDensity functional theory is commonly used in computational quantum mechanical investigations[\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. In this study, geometric calculations for all molecules were performed using Gaussian 09 software then generated and visualized their 3D molecular structures with GaussView 6.0 software[\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. Density Functional Theory (DFT)[\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e, \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e] was used and five input files for the reference molecule R (P3CPenT) were created using five different functionals named as MPW1PW91[\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e], B3LYP[\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e], WB97XD[\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e], PBEPBE[\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e] and CAM-B3LYP[\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]. This was done in order to optimize its structure and to minimize the risk of spin contamination in the results, basis set of 6-311G (d,p) and a restricted spin configuration was employed for the calculations.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eAfter optimizing the geometry, time-dependent self-consistent field calculations were conducted to obtain absorption spectra of the reference P3CPenT molecule in both gaseous and solvent state. The maximum absorption wavelengths (λ\u003csub\u003emax\u003c/sub\u003e) were compared from five different functionals (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) and found that the PBEPBE functional had a calculated λ\u003csub\u003emax\u003c/sub\u003e of 371.33 nm which was closest to the experimental λ\u003csub\u003emax\u003c/sub\u003e of 390 nm. As a result, PBEPBE was selected as the most suitable functional with a basis set of 6-311G (d,p). The absorption spectra for P3CPenT and P3CPenT-1 to P3CPenT-3 molecules were made using Origin 6.0 software[\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e] to analyze their ultraviolet-visible (UV-Vis) properties[\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e]. TD-SCF calculations were conducted using a preferred hybrid functional to predict the excited-state electronic behavior of molecules. The influence of the solvent (DMSO) on the maximum absorption wavelength (λ\u003csub\u003emax\u003c/sub\u003e) was analyzed using the polarizable continuum model (PCM)[\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e] with the integral equation formalism (IEFPCM)[\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e] as the computational approach. Additionally, the functional PBEPBE with level of theory 6-311G (d,p) was employed to analyze the density of states (DOS), frontier molecular orbitals (FMOs)[\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e] and transition density matrix (TDM)[\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e] in addition to conducting geometry optimization. This functional was also used to calculate oscillator strengths, dipole moments, ground-state energies, excited-state energies and electron transfer effects for the reference P3CPenT and designed P3CPenT-1 to P3CPenT-3 molecules.\u003c/p\u003e\u003cp\u003eMultiwfn 3.8[\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e] software was used to analyze the transition density matrix (TDM) which provided insights into the relocation of electron density between the excited and ground states of the molecules. Additionally, density of states (DOS)[\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e, \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e] plots were created using PyMOlyze 1.1[\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e] to visually represent the molecular orbitals and their energy levels. These analyses helped us gain a great understanding of transitions and the electronic structure in the reference P3CPenT and P3CPenT-1 to P3CPenT-3 molecules.\u003c/p\u003e"},{"header":"3. Results and Discussions","content":"\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\u003ch2\u003e3.1 Optimized Geometries\u003c/h2\u003e\u003cp\u003eThe geometries of reference and designed structures were optimized using the PBEPBE functional as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. The key factors for understanding charge transfer and self-aggregation properties are conjugation and planarity within the designed molecules which are enabled through the optimized geometries[\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e]. The central core adopted an out-of-plane position during the optimization process to reduce the potential energy of the acceptor (Cyano-based, Methoxy-based and Pyridine-based) groups, thiophene spacers and surface P3CPenT donors. Thiophene serves as a π-bridge and exhibits exceptional optoelectronic properties and high hole mobility, making it an attractive choice for designing advanced hole-transporting materials[\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e]. Acceptors are frequently employed to optimize energy levels and analyze photovoltaic performance.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFor every molecule, bond lengths and bond angles were computed. In particular, Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e displays the bond length (d1) and dihedral angle (θ1) between the P3CPenT donor and the bridge, and bond length (d2) and dihedral angle (θ2) between bridge and the acceptor groups. The bond lengths (d1 and d2) range from 1.507 \u0026Aring; to 1.417 \u0026Aring; suggesting the presence of double bonds and conjugation via π-electron delocalization. Furthermore, all molecules (P3CPenT-1, P3CPenT-2 and P3CPenT-3) had θ2 values ranging from 179.19 to -179.52 degrees indicating negligible steric restriction to the freedom of rotation of the acceptor units.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eDetermined bond lengths and dihedral angles for the reference molecule P3CPenT and its modified structures P3CPenT-1, P3CPenT-2, and P3CPenT-3\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"5\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eMolecules\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003ed1 (\u0026Aring;)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003ed2 (\u0026Aring;)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003eθ1 (deg)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e\u003cp\u003eθ2 (deg)\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e1.456\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.507\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e138.47\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e105.05\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e1.439\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.422\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e160.12\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e179.12\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e1.438\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.426\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e168.51\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e179.19\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT(3)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e1.438\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.417\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e167.98\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e-179.52\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\u003ch2\u003e3.2 Electronic properties\u003c/h2\u003e\u003cp\u003eFrontier molecular orbitals (FMOs) consist of the lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) and they play vital role to understand the electronic distribution in perovskite solar cells (PSCs). The HOMO located on the donor side resembles a valence band while the LUMO typically found on the acceptor side acts like a conduction band. The energy gap between LUMO and HOMO also known as band gap (Eg) is inversely related to molecular reactivity. Molecules with smaller band gaps tend to be softer, less stable and exhibit faster charge transport. The photovoltaic performance of perovskite solar cells is significantly influenced by LUMO and HOMO levels. In graphical representations, negative and positive phases of these orbitals are depicted by green and red colors, respectively.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe investigation of FMOs revealed that electron density was transferred across the entire structure in all designed compounds. A wider spatial distribution of HOMO and LUMO resulted in enhanced optical absorption. For P3CPenT at functional PBEPBE and basis set 6-311G (d,p) level, the ELUMO and EHOMO values were calculated as -2.0517 and \u0026minus;\u0026thinsp;5.0499 eV, respectively. The designed compounds P3CPenT-1, P3CPenT-2 and P3CPenT-3 showed EHOMO of -5.3264, -5.1718 and \u0026minus;\u0026thinsp;5.19367 eV, and ELUMO of -3.9361, -3.6814 and \u0026minus;\u0026thinsp;3.9549 eV with corresponding band gaps of 1.3903, 1.4904 and 1.2388 eV. In all molecules, HOMO density was mainly localized on the core (donor) while LUMO density was distributed across both the core and acceptor signifying effective intramolecular charge transfer.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eEstimated Eg values of the designed molecules at PBEPBE with 6-311G (d, p) level\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"4\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eMolecule\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eHOMO (eV)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eLUMO (eV)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003eEnergy gap (eV)\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e-5.0499\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e-2.0517\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e2.9982\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e-5.3264\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e-3.9361\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e1.3903\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e-5.1718\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e-3.6814\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e1.4904\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e-5.19367\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e-3.9549\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e1.2388\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e\u003ch2\u003e3.3 Optical Properties\u003c/h2\u003e\u003cp\u003eThe absorption spectrum is a significant tool for analyzing the optoelectronic properties of molecules. When a hole transport layer (HTL) absorbs radiation equal to its band gap energy, it transitions to an excited state. Critical parameters such as excitation energy (Ex), dipole moment (\u0026micro;), oscillator strength (f) and maximum absorption (λ\u003csub\u003emax\u003c/sub\u003e) are assessed to understand how these molecules utilize solar energy for efficient charge transfer. A molecule with high f, strong absorption at a higher molar absorption coefficient (ε) and low Ex is expected to exhibit significant intramolecular charge transfer (ICT). The following table displays the observed absorption profiles of compounds:\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eλ\u003csub\u003emax\u003c/sub\u003e, Ex, f, \u0026micro;\u003csub\u003eg\u003c/sub\u003e and LHE of reference and designed molecules studied in gaseous state\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"6\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eMolecule\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eCalculated λ\u003csub\u003emax\u003c/sub\u003e\u003c/p\u003e\u003cp\u003e(nm)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eExcitation energies Ex (eV)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003eOscillator strength (f)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e\u003cp\u003eDipole moment\u003c/p\u003e\u003cp\u003e\u0026micro;\u003csub\u003eg\u003c/sub\u003e (debye)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e\u003cp\u003eLHE\u003c/p\u003e\u003cp\u003e(1\u0026ndash;10\u003csup\u003e\u0026minus;\u0026thinsp;f\u003c/sup\u003e)\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e369.84\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e3.3524\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e0.1912\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e1.335575\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e0.3561\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e551.07\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e2.2499\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e0.7457\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e3.581910\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e0.8204\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e539.51\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e2.2981\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e0.8985\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e3.231796\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e0.8737\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e620.20\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.9991\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e0.8732\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e8.879381\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e0.8661\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eλ\u003csub\u003emax\u003c/sub\u003e, Ex, f, \u0026micro;\u003csub\u003eg\u003c/sub\u003e and LHE of reference and designed molecules with DMSO solvent\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"6\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eMolecule\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eCalculated λ\u003csub\u003emax\u003c/sub\u003e\u003c/p\u003e\u003cp\u003e(nm)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eExcitation energies Ex (eV)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003eOscillator strength (f)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e\u003cp\u003eDipole moment\u003c/p\u003e\u003cp\u003e\u0026micro;\u003csub\u003eg\u003c/sub\u003e (debye)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e\u003cp\u003eLHE\u003c/p\u003e\u003cp\u003e(1\u0026ndash;10\u003csup\u003e\u0026minus;\u0026thinsp;f\u003c/sup\u003e)\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e371.33\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e3.3389\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e0.3426\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e1.847061\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e0.5456\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e833.23\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.4880\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e0.8851\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e5.106566\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e0.8697\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e803.98\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.5421\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e0.6368\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e5.111522\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e0.7692\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e922.78\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.3436\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e0.8062\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e13.457676\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e0.8438\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eThe oscillator strength (f) is an important optical property of molecules, directly linked to the energy gap (Eg). The absorption spectrum was analyzed using PBEPBE with 6-311G (d,p) level of theory calculations. This analysis revealed that the efficiency of perovskite solar cells depends heavily on absorption characteristics. In the gaseous phase, the molecules P3CPenT, P3CPenT-1, P3CPenT-2 and P3CPenT-3 demonstrated the strongest configurations at PBEPBE with 6-311G (d,p) level. The molar absorption coefficient for the reference molecule P3CPenT was determined using various functionals along with the basis set of 6-311G (d,p). Since wavelength and energy gap are inversely correlated, a higher energy gap is expected to result in decreased charge carrier mobility and lower oscillator frequencies.\u003c/p\u003e\u003cp\u003eThe findings showed that P3CPenT-1 has a higher frequency and is significantly red-shifted than the reference P3CPenT. These specially created compounds showed an absorbance spectrum from 369.84 to 620.20 nm. The predicted P3CPenT wavelength was 369.84 nm but the projected compounds P3CPenT, P3CPenT-1, P3CPenT-2 and P3CPenT-3 had gaseous phase wavelengths of 369.84, 551.07, 539.51 and 620.20 nm respectively.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e\u003ch2\u003e3.4 Density of States (DOS)\u003c/h2\u003e\u003cp\u003eDensity of states gives us a picture at different energy levels of electronic states and it highlights the contributions from HOMO and LUMO across various excited states. This research is important for understanding how charges move, as it shows us where there are a lot of electronic states available for charge carriers in the energy spectrum. DOS calculations for P3CPenT and some newly designed molecules (P3CPenT-1, P3CPenT-2 and P3CPenT-3) were conducted using the functional PBEPBE with a basis set of 6-311G (d,p) level. In the DOS of P3CPenT, contributions from acceptor, core and donor can be seen indicated by red, green and blue lines respectively, with total DOS (TDOS) represented by a black line. The HOMO peaks are observed between \u0026minus;\u0026thinsp;5.0499 to -5.3264 eV while the LUMO peaks appear between \u0026minus;\u0026thinsp;2.0517 to -3.9549 eV. The region without peaks between the HOMO and LUMO levels represents the energy gap (Eg).\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\u003ch2\u003e3.5 Molecular Electrostatic Potential (MEP)\u003c/h2\u003e\u003cp\u003eMEP is significant for understanding how electric charges are distributed within a molecule and how they move. In polymer solar cells (PSCs), the MEP is crucial for processes like charge transport, separation and recombination, which all affect the efficiency of solar cells. This study examines the MEP of P3CPenT and its derivatives (P3CPenT-1, P3CPenT-2 and P3CPenT-3) to analyze how charges are spread out. The MEP helps to identify areas with an excess of electrons and areas lacking electrons within the molecule, showing where the molecule is most reactive. MEP maps use a color gradient, ranging from dark blue (positive potential) to red (very negative potential), to visually represent these areas.\u003c/p\u003e\u003cp\u003eThe electrostatic maps shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e illustrate the three-dimensional distribution of charges within the molecules. The core of the P3CPenT molecule is depicted in a yellowish color while the designed molecules exhibit a blue tint around the core indicating the presence of acceptor units. This blue color shows that the acceptor units have the ability to attract electrons. Additionally, the color gradient on the maps represents electronegativity with red indicating areas of high electronegativity. The presence of red areas around P3CPenT-1, P3CPenT-2 and P3CPenT-3 indicates an increase in electron density around the acceptor units which contain electronegative elements such as nitrogen and oxygen.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e\u003ch2\u003e3.6 Transition Density Matrix (TDM)\u003c/h2\u003e\u003cp\u003eIt is important to analyze holes in matter in order to understand processes such as separation, diffusion and charge excitation. In this study, the charge transfer matrix, hole-electron distribution and transition density matrix (TDM) were simulated to explore charge transfer mechanisms in designed hole transport materials (HTMs). Heat maps of TDM and charge transfer matrix provided insights into the interactions between acceptor and donor core moieties during excitation. The mapping of hole-electron distribution revealed spatial overlap and contributions from both holes and electrons with the TDM maps indicating higher contributions from TPA groups and substituted acceptors. The designed HTMs demonstrated excellent charge transfer coherence and consistent charge generation while low coupling and increased charge separation suggested favorable conditions for efficient charge transport.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e\u003ch2\u003e3.7 Analyzed Parameters\u003c/h2\u003e\u003cp\u003eV\u003csub\u003eoc\u003c/sub\u003e is the maximum voltage attained when there is no external current flowing. One can determine V\u003csub\u003eoc\u003c/sub\u003e using equation given as follows:\u003c/p\u003e\u003cp\u003eV\u003csub\u003eoc\u003c/sub\u003e = (|E\u003csub\u003eHOMO\u003c/sub\u003e of donor - E\u003csub\u003eLUMO\u003c/sub\u003e of acceptor|)/e \u0026minus;\u0026thinsp;0.3\u003c/p\u003e\u003cp\u003ewhere V\u003csub\u003eoc\u003c/sub\u003e represents the maximum voltage output when no current flows through the circuit and a factor of 0.3 is introduced as a practical adjustment to account for real-world conditions. Furthermore, it is assumed that the generated molecules in this computational study work have a standard charge of 1 (so e\u0026thinsp;=\u0026thinsp;1).\u003c/p\u003e\u003cp\u003eThe fill factor (FF) is a crucial performance parameter with theoretical values generally exceeding those obtained experimentally. It is determined using the following equation:\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:FF\\:=\\frac{\\frac{eVoc\\:}{{K}_{B}\\:T}\\:-\\:ln(\\frac{e{V}_{oc}}{{K}_{B}T}+0.72)}{\\frac{eVoc\\:}{{K}_{B}\\:\\text{T}}+1}$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eIn Table\u0026nbsp;\u003cspan refid=\"Tab5\" class=\"InternalRef\"\u003e5\u003c/span\u003e, the values of J\u003csub\u003esc,\u003c/sub\u003e V\u003csub\u003eoc\u003c/sub\u003e and FF can be found where the values were obtainedby using PC\u003csub\u003e61\u003c/sub\u003eBM as the acceptor and our studied compounds as donors. P3CPenT is expected to have HOMO and LUMO values of -5.0499 and \u0026minus;\u0026thinsp;2.0517 eV respectively. By using the LUMO of the PC\u003csub\u003e61\u003c/sub\u003eBM acceptor, the V\u003csub\u003eoc\u003c/sub\u003e values based on the HOMO values of our proposed molecules were estimated. Js\u003csub\u003ec\u003c/sub\u003e was calculated to be 21.3117 as reported in the reference literature and we compared our created molecules to this value. This comparison helps us to assess the impact on power conversion efficiency (PCE) of the specified molecules. PCE and J\u003csub\u003eSC\u003c/sub\u003e are directly related.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe newly designed molecules P3CPenT-1 and P3CPenT-3 demonstrate a higher open-circuit voltage (V\u003csub\u003eoc\u003c/sub\u003e) than the original P3CPenT molecule. This improvement in voltage generation is significant and is attributed to a greater shift in their LUMO energy levels. The PCE of the designed molecules is determined by the fill factor (FF) of designed molecules. The key factors influencing PSC performance such as electrical characteristics like short-circuit current density J\u003csub\u003esc\u003c/sub\u003e, open circuit voltage (V\u003csub\u003eoc\u003c/sub\u003e), normalized V\u003csub\u003eoc\u003c/sub\u003e, fill factor (FF) and power conversion efficiency (PCE)% can be used to derive this value which has no dimensions.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab5\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 5\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eOptimized photovoltaic performances of the P3CPenT\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"7\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eMolecule\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eJ\u003csub\u003esc\u003c/sub\u003e(mA/cm\u003csup\u003e2\u003c/sup\u003e)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eV\u003csub\u003eoc\u003c/sub\u003e(eV)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003eNormalized V\u003csub\u003eoc\u003c/sub\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e\u003cp\u003eFF\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e\u003cp\u003eFF%\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c7\"\u003e\u003cp\u003ePCE%\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e21.3117\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.0499\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e63.7643\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e0.9202\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e92.02\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e\u003cp\u003e20.5896\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e21.3117\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.3264\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e51.2618\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e0.9053\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e90.53\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e\u003cp\u003e25.5909\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e21.3117\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.1718\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e45.2870\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e0.8957\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e89.57\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e\u003cp\u003e22.3683\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eP3CPenT-3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e21.3117\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1.1937\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e46.1333\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e0.8972\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e89.72\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e\u003cp\u003e22.8246\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThe P3CPenT-based hole transport materials (HTMs) and their derivatives have proven to be highly promising candidates for use in perovskite solar cells. Among these, P3CPenT-1 achieved remarkable power conversion efficiency (PCE) of 25.59%, significantly outperforming the widely used Spiro-OMeTAD (~\u0026thinsp;20\u0026ndash;21%) under comparable conditions. This enhanced performance was attributed to its optimized open-circuit voltage (V\u003csub\u003eoc\u003c/sub\u003e = 1.3264 eV), high fill factor (FF\u0026thinsp;=\u0026thinsp;90.53%) and reduced energy gap (1.3903 eV) which collectively ensure improved charge transport and minimized energy losses. The alignment of LUMO level of P3CPenT-1 (-3.9361 eV) with the conduction band of perovskite absorber facilitated proficient electron blocking while its HOMO level (-5.3264 eV) supported effective hole extraction. Additionally, P3CPenT derivatives exhibited superior thermal stability, chemical durability and cost-effective synthesis compared to conventional HTMs like Spiro-OMeTAD. These findings highlighted the potential of P3CPenT-based HTMs as stable, efficient and scalable alternatives for advancing next-generation photovoltaic technologies, offering a sustainable path toward high-performance solar energy conversion.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eFunding\u003c/h2\u003e\u003cp\u003eThis research was funded by the Higher Education Commission (HEC) of Pakistan [Grant No: 8615/Punjab/NRPU/R\u0026amp;D/HEC/2017].\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eN.F. conceived and designed the study, collected and managed the data, performed the analysis and interpretation, and drafted the manuscript. K.A. (corresponding author, [email protected]) supervised the project and provided critical feedback and revisions. The final manuscript was reviewed and approved by both authors.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eThis work was supported by the Higher Education Commission (HEC) of Pakistan [Grant No: 8615/Punjab/NRPU/R\u0026amp;D/HEC/2017]. The authors also would like to acknowledge Prof. Khurshid Ayub, Comsats University Islamabad, Abbottabad Campus, Pakistan.\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eThe datasets analysed and generated during the current study, including DFT output files and processed data are available in the Zenodo repository, [https://doi.org/10.5281/zenodo.17331313](https:/doi.org/10.5281/zenodo.17331313) .\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eKannan, N. \u0026amp; Vakeesan, D. Solar energy for future world: - A review. \u003cem\u003eRenew. Sustain. 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Recent Advances in Organic Hole Transporting Materials for Perovskite Solar Cells. \u003cem\u003eSol RRL\u003c/em\u003e, \u003cb\u003e4\u003c/b\u003e, 12, (2020).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Density functional theory (DFT), Perovskites, Thiophene, Optimization, Optoelectronic properties","lastPublishedDoi":"10.21203/rs.3.rs-7659823/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7659823/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eOrganic and perovskite solar cells have fascinated world because of their excellent charge carrier mobility, ease of fabrication and high power conversion efficiency. This study has focused on the molecular design of hole-transporting materials (HTMs) using P3CPenT as a reference molecule for perovskite solar cells. Newly designed small molecules are evaluated using DFT with different functionals (WB97XD, CAM-B3LYP, PBEPBE, MPW1PW91 and B3LYP) with basis set 6-311G (d,p) in GaussView 6.0 and Gaussian 09W. Key properties such as absorption spectra, HOMO-LUMO energy gaps and excitation energies are analyzed. Molecular optimization and energy gap graphs are generated using Origin 6.0. These results have highlighted the potential of these molecules as HTMs with promising implications for enhancing solar cell performance.\u003c/p\u003e","manuscriptTitle":"Optimization of P3CPenT-Based Hole Transport Layers to Boost Efficiency in Perovskite Solar Cells","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-10-29 08:59:33","doi":"10.21203/rs.3.rs-7659823/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"e4bd810e-949d-41fe-b7d6-7a19f26f9b4b","owner":[],"postedDate":"October 29th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":56910086,"name":"Physical sciences/Chemistry"},{"id":56910087,"name":"Physical sciences/Energy science and technology"},{"id":56910088,"name":"Physical sciences/Materials science"},{"id":56910089,"name":"Physical sciences/Physics"}],"tags":[],"updatedAt":"2025-11-12T08:24:16+00:00","versionOfRecord":[],"versionCreatedAt":"2025-10-29 08:59:33","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7659823","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7659823","identity":"rs-7659823","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}