Interface engineering of p-n heterojunction for kesterite photovoltaics:A progress review

Kesterite Cu_(2)ZnSn(S,Se)_4(CZTSSe)is considered one or the most promising thin-film photovoltaic(PV)technologies due to its bandgap tunability(1.0~1.5 eV)and high absorption coefficient(>10^(4)cm^(-1)).However,the highest power conversion efficiency(PCE)of CZTSSe has so far only reached up to 12.6%,much lower than the theoretical limit defined by the Shockley-Queisser(SQ)theory.The large opencircuit voltage(V_(oc))deficit and inferior fill factor(FF)are prevalent in kesterite PV and hamper the improvement in efficiency.In this review,unfavourable energy band alignment at the CZTSSe/buffer junction,as well as defective interface are identified as two obstacles at the p-n heterojunction.These issues contribute to the interface induced recombination,thus significantly reducing efficiency.Subsequently,we review recent advances in strategies to improve the efficiency by altering the characteristics of the interface,covering alternative buffer layers,heterojunction treatments and passivation layers.Finally,future research directions of heterojunction engineering are proposed as schemes towards the ideal interface in kesterite solar cells.

Path towards high-efficient kesterite solar cells

Kesterite structure semiconductor Cu2ZnSn（S,Se）4 is one of the most promising candidate as a light absorber material to overtake the next generation of thin film solar cells, owing to its low cost, non-toxic, and earth abundant source materials. The Sbockley-Queisser limit of the single junction Cu2ZnSn（S,Se）4 solar cell is over 30%, signifying a large potential of this family of solar cells. In the past years, with the development of synthesis techniques, Cu2ZnSn（S,Se）4 solar cells have attracted considerable atten- tion and the power conversion efficiency of Cu2ZnSn（S,Se）4 solar cell has experienced a rapid progress. Presently, the certified champion efficiency of CZTSSe solar cells has reached to 12.6%, which is far below the efficiency of Cu（ln,Ga）Se2 solar cell. In this review, the developments of Cu2ZnSn（S,Se）4 solar cells in recent years are briefly reviewed. Then the fundamental understanding of Cu2ZnSn（S,Se）4 solar cells is introduced, including materials and device structure, as well as the band alignment of hetero-junction and their impacts on device performance. After that, we mainly review the progress and achievements in the preparation processes, through vacuum and non-vacuum based processes. Finally, we outline the challenges and perspectives of this promising solar cell.

Interfaces of high-efficiency kesterite Cu_2ZnSnS(e)_4 thin film solar cells

Cu2ZnSnS（e）4 （CZTS（e）） solar cells have attracted much attention due to the elemental abundance and the non- toxicity. However, the record efficiency of 12.6% for CuzZnSn（S,Se）4 （CZTSSe） solar cells is much lower than that of Cu（In,Ga）See （CIGS） solar cells. One crucial reason is the recombination at interfaces. In recent years, large amount inves- tigations have been done to analyze the interfacial problems and improve the interfacial properties via a variety of methods. This paper gives a review of progresses on interfaces of CZTS（e） solar cells, including： （i） the band alignment optimization at buffer/CZTS（e） interface, （ii） tailoring the thickness of MoS（e）2 interfacial layers between CZTS（e） absorber and Mo back contact, （iii） the passivation of rear interface, （iv） the passivation of front interface, and （v） the etching of secondary phases.

Identifying the relationships between subsurface absorber defects and the characteristics of kesterite solar cells

Understanding the defect characteristics that occur near the space-charge regions(SCRs)of kesterite(CZTSSe)solar cells is important because the recombination loss at the CZTSSe/CdS interface is considered the main cause of their low efficiency.CZTSSe surfaces with different elemental compositions were formed without polishing(C00)and with polishing for 20 s(C20)and 60 s(C60).For C60,a specific region near the SCR was excessively Cu-rich and Zn-poor compared to C00 and C20.Various charged defects formed where the elemental variation was large.As the main deep acceptor defect energy level(E_(a2))near the SCR increased,the efficiency,open-circuit voltage deficit,and current density degraded,and this phenomenon was especially rapid for large E_(a2) values.As the E_(a2) near the SCR became deep,the carrier diffusion length decreased more for the CZTSSe solar cells with a low carrier mobility than for the CuInGaSe_(2)(CIGSe)solar cells.The large amplitude of the electrostatic potential fluctuation in the CZTSSe solar cells induced a high carrier recombination and a short carrier lifetime.Consequently,the properties of the CZTSSe solar cells were more strongly degraded by defects with deep energy levels near the SCR than those of the CIGSe solar cells.

Theoretical study on the kesterite solar cells based on Cu_2ZnSn(S,Se)_4 and related photovoltaic semiconductors

The kesterite thin film solar cells based on the quaternary Cu2ZnSnS4 and Cu2ZnSnSe4 and their alloys Cu2ZnSn（S,Se）4 have been considered as environment-friendly and non-toxic alternatives to the currently commercialized CdTe and Cu（In,Ga）Se2 thin film solar cells. From the theoretical point of view, we will review how the group I2-II-IV-VI4 quaternary compound semiconductors are derived from the binary CdTe and the ternary CuInSe2 or CuGaSe2 through the cation mutation, and how the crystal structure and electronic band structure evolve as the component elements change. The increased structural and chemical freedom in these quaternary semiconductors opens up new possibility for the tailoring of material properties and design of new light-absorber semiconductors. However, the increased freedom also makes the development of high-efficiency solar cells more challenging because much more intrinsic point defects, secondary phases, surfaces, and grain-boundaries can exist in the thin films and influence the photovoltaic performance in a way different from that in the conventional CdTe and Cu（In,Ga）Se2 solar cells. The experimental characterization of the properties of defects, secondary phase, and grain-boundaries is currently not very efficient and direct, especially for these quaternary compounds. First-principles calculations have been successfully used in the past decade for studying these properties. Here we will review the theoretical progress in the study of the mixed-cation and mixed-anion alloys of the group I2-II-IV- VI4 semiconductors, defects, alkaline dopants, and grain boundaries, which provided very important information for the optimization of the kesterite solar cell performance.

Potassium doping for grain boundary passivation and defect suppression enables highly-efficient kesterite solar cells

The complicated and diverse deep defects,voids,and grain boundary in the CZTSSe absorber are the main reasons for carrier recombination and efficiency degradation.The further improvement of the open-circuit voltage and fill factor so as to increase the efficiency of CZTSSe device is urgent.In this work,we obtained K-doped CZTSSe absorber by a simple solution method.The medium-sized K atoms,which combine the advantages of light and heavy alkali metals,are able to enter the grain interior as well as segregate at grain boundary.The K-Se liquid phase can improve the absorber crystallinity.We find that the accumulation of the wide bandgap compound K_(2)Sn_(2)S_(5)at grain boundary can increase the contact potential difference of grain boundary,form more effective hole barriers,and enhance the charge separation ability.At the same time,K doping passivates the interface as well as bulk defects and suppresses the non-radiative recombination.The improved crystallinity,enhanced charge transport capability and reduced defect density due to K doping result in a significant enhancement of the carrier lifetime,leading to 13.04%device efficiency.This study provides a new idea for simultaneous realization of grain boundary passivation and defect suppression in inorganic kesterite solar cells.

A review of recent advances of kesterite thin films based on magnesium,iron and nickel for photovoltaic application:insights into synthesis,characterization and optoelectronic properties

This review emphasizes the recent advancements and prospects of thin-film kesterite-based photovoltaic(PV)applications using magnesium,iron and nickel.The quest for novel materials employed in solar cells has resulted in incorporating these elements into the composition of kesterite as substitutes or modifiers(dopants)for zinc.This integration has induced notable repercussions on the structural,optoelectronics and morphological properties,which are reviewed.The first section of this paper offers a comprehensive review of the general characteristics of kesterite minerals.These crucial materials exhibit a high absorption coefficient(104 cm-1)and an optical band gap of 1.0-1.8 eV.Moreover,they are free of critical raw materials,non-toxic and sustainable.The second section depicts the substitution or modification of zinc by magnesium in kesterite.Additionally,this paper provides a comprehensive review of the quaternary and pentanary systems Cu_(2)MgSn(S,Se)_(4) and Cu_(2)Zn_(1-x)Mg_(x)SnS_(4),highlighting their advantages and drawbacks.In the last section,a review of the quaternary or pentanary systems is conducted,namely Cu_(2)ZnxFe_(1-x)SnS_(4) and Cu_(2)ZnxNi_(1-x)SnS_(4),along with their effects on optoelectronic properties.In conclusion,various methods for obtaining modified or substituted kesterite materials using magnesium,iron and nickel have demonstrated sustainability,scalability for industrial production and potential candidacy as substitutes for conventional PV materials.The prospects for pentanary materials(Cu_(2)Zn_(1-x)Mg_(x)SnS_(4),Cu_(2)Zn_(1-x)FexSnS_(4) and Cu_(2)Zn_(1-x)NixSnS_(4))are to overcome the efficiency record of kesterite reported in 2014,which was 12.6%for Cu_(2)ZnSn(S,Se)_(4),and to enhance its optoelectronic properties through synthesis conditions that comply with the principles of green chemistry.

Coordination engineering of Cu-Zn-Sn-S aqueous precursor for efficient kesterite solar cells

Aqueous precursors provide an alluring approach for low-cost and environmentally friendly production of earth-abundant Cu2ZnSn(S,Se)4(CZTSSe)solar cells.The key is to find an appropriate molecular agent to prepare a stable solution and optimize the coordination structure to facilitate the subsequent crystallization process.Herein,we introduce thioglycolic acid(TGA),which possesses strong coordination(SH)and hydrophilic(COOH)groups,as the agent and use deprotonation to regulate the coordination competition within the aqueous solution.Ultimately,metal cations are adequately coordinated with thiolate anions,and carboxylate anions are released to become hydrated to form an ultrastable aqueous solution.These factors have contributed to achieving CZTSSe solar cells with an efficiency as high as 12.3%(a certified efficiency of 12.0%)and providing an extremely wide time window for precursor storage and usage.This work represents significant progress in the non-toxic solution fabrication of CZTSSe solar cells and holds great potential for the development of CZTSSe and other metal sulfide solar cells.

Sn precursor enables 12.4%efficient kesterite solar cell from DMSO solution with open circuit voltage deficit below 0.30 V

The limiting factor preventing further performance improvement of the kesterite(sulfide Cu2ZnSnS4(CZTS),selenide Cu2ZnSnS4(CZTSe),and their alloying Cu2Zn Sn(S,Se)4(CZTSSe))thin film solar cells is the large open-circuit voltage deficit(Voc,def)issue,which is 0.345 V for the current world record device with an efficiency of 12.6%.In this study,SnCl4 and Sn Cl2·2H2O were respectively used as tin precursor to investigate the Voc,def issue of dimethyl sulfoxide(DMSO)solution processed CZTSSe solar cells.Different complexations of tin compounds with thiourea(Tu)and DMSO resulted in different reaction pathways from the solution to the absorber material and thus dramatic differences in photovoltaic performance.The coordination of Sn^2+with Tu led to the formation of SnS,ZnS and Cu2S in the precursor film,which converted to selenides first and then fused to CZTSSe,resulting in poor film quality and device performance.The highest efficiency obtained from this film was 8.84%with a Voc,def of 0.391 V.The coordination of Sn4+with DMSO facilitated direct formation of CZTS phase in the precursor film which directly converted to CZTSSe during selenization,resulting in compositional uniform absorber and high device performance.A device with an active area efficiency of 12.2%and a Voc,def of 0.344 V was achieved from the Sn^4+solution processed absorber.Furthermore,CZTSSe/Cd S heterojunction heat treatment(JHT)significantly improved the performance of the Sn^4+device but had slightly negative effect on the Sn2+device.A champion CZTSSe solar cell with a total area efficiency of 12.4%(active area efficiency of 13.6%)and a low Voc,def of 0.297 V was achieved from the Sn^4+solution.Our results demonstrate the preformed uniform CZTSSe phase enabled by Sn4+precursor is the key for the highly efficient CZTSSe absorber.The lowest Voc,def and high efficiency achieved here shines new light on the future of CZTSSe solar cell.

Self-powered broadband kesterite photodetector with ultrahigh specific detectivity for weak light applications

Kesterite Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)is a promising candidate for photodetector(PD)applications thanks to its excellent optoelectronic properties.In this work,a green solution-processed spin coating and selenization-processed thermodynamic or kinetic growth of high-quality narrow bandgap kesterite CZTSSe thin film is developed.A self-powered CZTSSe/CdS thin-film PD is then successfully fabricated.Under optimization of light absorber and heterojunction interface,especially tailoring the defect and carrier kinetics,it can achieve broadband response from300 to 1300 nm,accompaniedwith a high responsivity of 1.37A/W,specific detectivity(D*)up to 4.0×10^(14)Jones under 5 nW/cm^(2),a linear dynamic range(LDR)of 126 dB,and a maximum Ilight/Idark ratio of 1.3×10^(8)within the LDR,and ultrafast response speed(rise/decay time of 16 ns/85 ns),representing the leading-level performance to date,which is superior to those of commercial andwell-researched photodiodes.Additionally,an imaging system with a 905nm laser is built for weak light response evaluation,and can respond to 718 pW weak light and infrared imaging at a wavelength as low as 5 nW/cm2.It has also been employed for photoplethysmography detection of pulsating signals at both the finger and wrist,presenting obvious arterial blood volume changes,demonstrating great application potential in broadband and weak light photodetection scenarios.

Recent progress in defect engineering for kesterite solar cells

Kesterite Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)thin film solar cells have been regarded as one of the most promising thin film photovoltaic technologies,offering a low-cost and environmentally friendly solar energy option.Although remarkable advances have been achieved in kesterite solar cells,the performance gap relative to mature thin film photovoltaic technologies such as CIGSe and Cd Te remains large.Significant open-circuit voltage(V_(OC))deficit has been recognized as the main limiting factor to performance improvement,with undesirable intrinsic defects being a key culprit contributing to the low V_(OC).To realize the promise inherent in kesterite CZTS to become an earth-abundant alternative to existing thin film photovoltaic technologies with comparable performance,significant research effort has been invested to tackle the challenging defect issues.In this review,recent progress and achievements relevant to engineering improvements to the defect properties of the semiconductor have been examined and summarized.Promising strategies include:(i)manipulating the synthesis process to obtain a desirable reaction pathway and chemical environment;(ii)introducing cation substitution to increase the ionic size difference and supress the related band tailing deep-level defects;(iii)applying post deposition treatment(PDT)with alkaline elements to passivate the detrimental defects.These advances obtained from work on kesterite solar cells may lead to future high performance from this material and may be further extended to other earth-abundant chalcogenide photovoltaic technologies.

Impact of oxygen incorporation on interface optimization and defect suppression for efficiency enhancement in Cu_(2)ZnSn(S,Se)_(4)solar cells

Kesterite Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells suffer from severe carrier recombination,limiting the photovoltaic performance.Unfavorable energy band alignment at the p-n junction and defective front interface are two main causes.Herein,oxygen incorporation in CZTSSe via absorber air-annealing was developed as a strategy to optimize its surface photoelectric property and reduce the defects.With optimized oxygen incorporation conditions,the carrier separation and collection behavior at the front interface of the device is improved.In particular,it is found that oxygen incorporated absorber exhibits increased band bending,larger depletion region width,and suppressed absorber defects.These indicate the dynamic factors for carrier separation become stronger.Meanwhile,the increased potential difference between grain boundaries and intra grains combined with the decreased concentration of interface deep level defect in the absorber provide a better path for carrier transport.As a consequence,the champion efficiency of CZTSSe solar cells has been improved from 9.74%to 12.04%with significantly improved open-circuit voltage after optimized air-annealing condition.This work provides a new insight for interface engineering to improve the photoelectric conversion efficiency of CZTSSe devices.

Surface defect ordered Cu_(2)ZnSn(S,Se)_(4) solar cells with efficiency over 12% via manipulating local substitution

The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.

Novel two-step CdS deposition strategy to improve the performance of Cu2ZnSn(S,Se)4 solar cell

Kesterite Cu2ZnSn(S,Se)4(CZTSSe)solar cells have drawn worldwide attention for their promising photovoltaics performance and earth-abundant element composition,yet the record efficiency of this type of device is still far lower than its theoretical conversion efficiency.Undesirable band alignment and severe non-radiative recombination at CZTSSe/CdS heterojunction interfaces are the major causes limiting the current/voltage output and overall device performance.Herein,we propose a novel two-step CdS deposition strategy to improve the quality of CZTSSe/CdS heterojunction interface and thereby improve the performance of CZTSSe solar cell.The two-step strategy includes firstly pre-deposits CdS thin layer on CZTSSe absorber layer by chemical bath deposition(CBD),followed with a mild heat treatment to facilitate element inter-diffusion,and secondly deposits an appropriate thickness of CdS layer by CBD to cover the whole surface of pre-deposited CdS and CZTSSe layers.The solar energy conversion efficiency of CZTSSe solar cells with two-step deposited CdS layer approaches to 8.76%(with an active area of about 0.19 cm2),which shows an encouraging improvement of over 87.98%or 30.16%compared to the devices with traditional CBD-deposited CdS layer without and with the mild annealing process,respectively.The performance enhancement by the two-step CdS deposition is attributed to the formation of more favorable band alignment at CZTSSe/CdS interface as well as the effective decrease in interfacial recombination paths on the basis of material and device characterizations.The two-step CdS deposition strategy is simple but effective,and should have large room to improve the quality of CZTSSe/CdS heterojunction interface and further lift up the conversion efficiency of CZTSSe solar cells.

Structural and electrical characterization of Cu_(2)ZnSnS_(4) ingot material grown by melting method

In this work,a Cu_(2)ZnSnS_(4)(CZTS)ingot is grown via a melting method,then cooled;the resulting molten stoichiomet-ric mixture is sealed off in a quartz ampoule under vacuum.The CZTS powder chemical composition analyses are determined us-ing energy dispersive spectroscopy,and revealing the slightly Cu-rich and Zn-poor character of the ingot.Powder X-ray diffrac-tion analysis reveals a crystalline structure with a kesterite phase formation,and a preferred orientation of(112)plane.The lat-tice constants of the a-and c-axes,calculated based on the XRD analyses,are a=5.40Åand c=10.84Å.Based on Hall measure-ments at room temperature,we find that the crystal exhibits p-type conductivity,with a high concentration of 1018 cm^(-3),a res-istivity of 1.7Ωcm,and a mobility of 10.69 cm^(2)V-1s-1.Activation energies are estimated based on an Arrhenius plot of conductiv-ity versus 1/T,for a temperature range of 80-350 K,measuring 35 and 160 meV in low-and high-temperature regimes,respect-ively,which is attributed to complex defects(2CuZn+SnZn)and antisite defects(CuZn),respectively.The observed scattering mech-anisms are attributed to ionized impurities and acoustic phonons at low and high temperatures,respectively.The extracted band-gap is 1.37 eV.

Colloidal synthesis and characterization of Cu_2ZnSnS_4 nanoplates

Synthesis of copper zinc tin sulphide（Cu_2ZnSnS_4/ with nanoplate morphology was achieved through colloidal method using oleic acid as capping agent and solvent with 1-octadecene（1-ODE） at 240°C.X-ray diffraction（XRD） analysis shows that the synthesized nanoplates possessed pure kesterite phase.SEM analysis clearly shows the formation of nanoplates having the size of about 50–100 nm.Electron spin resonance（ESR） spectrum analysis of the prepared nanoplates shows that the valence state of copper（II） which indicates the strong coupling with other metal ions.Thermo gravimetric/differential thermal analysis（TG/DTA） analysis shows the weight loss of sample at 450°C predicting the loss of capping ligands on the surface of the nanoparticles.The possible mechanism for the conversion of nanoplate-like structures during synthesis was discussed.The results are discussed in detail.

11.39%efficiency Cu_(2)ZnSn(S,Se)_(4) solar cells from scrap brass

Kesterite Cu2ZnSn(S,Se)4(CZTSSe)is one of the most promising next-generation thin-film photovoltaic materials due to its environmental friendliness and earthabundant constitutions,excellent optoelectronic properties(high absorption coefficient>104/cm and tunable band gap 1.0–1.5 eV)and high theoretical efficiency(32%).1,2 In 2014,12.6%3 efficiency was achieved by the IBM group using the hydrazine method.Based on the sputtering process,12.62%4 efficiency for CZTSSe and 12.5%5 efficiency for CZTSe have been achieved in recent years.However,the highest efficiency has stuck around 12.6%for several years.Lately,a breakthrough with certified 13%power conversion efficiency(PCE)has been demonstrated for CZTSSe thin-film solar cells,surpassing the dust-covered efficiency record since 2014.3,6 Along with the efficiency advancement of kesterite solar cells,a cost-effective fabrication process with low carbon footprint plays an increasingly important role considering the near-future industrialisation of this kind of solar cell with low energy payback time.