In-doping collaboratively controlling back interface and bulk defects to achieve efficient flexible CZTSSe solar cells

Focusing on the low open circuit voltage(V_(OC))and fill factor(FF)in flexible Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells,indium(In)ions are introduced into the CZTSSe absorbers near Mo foils to modify the back interface and passivate deep level defects in CZTSSe bulk concurrently for improving the performance of flexible device.The results show that In doping effectively inhibits the formation of secondary phase(Cu(S,Se)_(2))and VSndefects.Further studies demonstrate that the barrier height at the back interface is decreased and the deep level defects(Cu_(Sn)defects)in CZTSSe bulk are passivated.Moreover,the carrier concentration is increased and the V_(OC) deficit(V_(OC,def))is decreased significantly due to In doping.Finally,the flexible CZTSSe solar cell with 10.01%power conversion efficiency(PCE)has been obtained.The synergistic strategy of interface modification and bulk defects passivation through In incorporation provides a new thought for the fabrication of efficient flexible kesterite-based solar cells.

Effect of substrate temperature and oxygen plasma treatment on the properties of magnetron-sputtered CdS for solar cell applications

Cadmium sulfide(CdS)is an n-type semiconductor with excellent electrical conductivity that is widely used as an electron transport material(ETM)in solar cells.At present,numerous methods for preparing CdS thin films have emerged,among which magnetron sputtering(MS)is one of the most commonly used vacuum techniques.For this type of technique,the substrate temperature is one of the key deposition parameters that affects the interfacial properties between the target film and substrate,determining the specific growth habits of the films.Herein,the effect of substrate temperature on the microstructure and electrical properties of magnetron-sputtered CdS(MS-CdS)films was studied and applied for the first time in hydrothermally deposited antimony selenosulfide(Sb_(2)(S,Se)_(3))solar cells.Adjusting the substrate temperature not only results in the design of the flat and dense film with enhanced crystallinity but also leads to the formation of an energy level arrangement with a Sb_(2)(S,Se)_(3)layer that is more favorable for electron transfer.In addition,we developed an oxygen plasma treatment for CdS,reducing the parasitic absorption of the device and resulting in an increase in the short-circuit current density of the solar cell.This study demonstrates the feasibility of MS-CdS in the fabrication of hydrothermal Sb_(2)(S,Se)_(3)solar cells and provides interface optimization strategies to improve device performance.

p型“SE+PERC”双面太阳电池背面工艺对光伏组件PID效应的影响研究

基于p型“SE+PERC”双面太阳电池的背面工艺,针对背表面抛光状态、背面氧化铝薄膜厚度、背面膜层结构、背面氮化硅薄膜折射率几个因素对光伏组件电势诱导衰减(PID)效应的影响进行了研究。研究结果表明:1)背表面抛光状态越光滑,对应制备的光伏组件在PID测试后的输出功率损失率越小;2)背面氧化铝薄膜厚度为10 nm及以上时对应制备的光伏组件在PID测试后的输出功率损失率差异不大;3)背面膜层结构对PID效应存在影响,合理设计背面膜层结构可以有效抑制光伏组件PID效应;4)背面氮化硅薄膜折射率大于等于2.10时,对应制备的光伏组件在PID测试后的输出功率损失率降至2.00%以内且可以稳定保持在较低水平。研究结果可为p型“SE+PERC”双面太阳电池背面工艺优化提供指导方向。

管式PECVD工艺对“SE+PERC”晶体硅太阳电池镀膜均匀性的影响及改善研究

针对在“SE+PERC”晶体硅太阳电池制备过程中,采用管式等离子体增强化学气相沉积(PECVD)工艺沉积正面钝化介质膜后,硅片正面会出现角部发红色差,即镀膜均匀性异常的问题,通过实验,对硅片厚度、工器具状态、背面膜层结构、正面钝化介质膜沉积工艺等影响因素对硅片正面角部发红色差的影响分别进行分析和讨论,并提出解决方案。研究结果表明:硅片正面角部发红色差的产生与硅片自身厚度、工器具状态、背面膜层结构、正面钝化介质膜沉积工艺均存在一定关系。通过采用最具优势的管式PECVD工艺条件,即优化自动化装片技术、控制石墨舟形变量、采用合适的背面膜层结构,以及正面钝化介质膜沉积工艺采用高射频功率叠加高腔体压力,可将正面角部发红色差硅片的占比降低至0%,从而可有效提升“SE+PERC”晶体硅太阳电池的成品率,提升生产线的经济效益。

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.

Precisely tuning Ge substitution for efficient solution-processed Cu_2ZnSn(S,Se)_4 solar cells

The kesterite Cu2ZnSn（S,Se）4 （CZTSSe） solar cells have yielded a prospective conversion efficiency among all thin- film photovoltaic technology. However, its further development is still hindered by the lower open-circuit voltage （Voc）, and the non-ideal bandgap of the absorber is an important factor affecting this issue. The substitution of Sn with Ge provides a unique ability to engineer the bandgap of the absorber film. Herein, a simple precursor solution approach was successfully developed to fabricate Cu2Zn（SnyGel_y）（SxSe~ x）4 （CZTGSSe） solar cells. By precisely adjusting the Ge content in a small range, the Voc and Jsc are enhanced simultaneously. Benefitting from the optimized bandgap and the maintained spike structure and light absorption, the 10% Ge/（Ge＋Sn） content device with a bandgap of approximately 1.1 eV yields the highest efficiency of 9.36%. This further indicates that a precisely controlled Ge content could further improve the cell performance for efficient CZTGSSe solar cells.

Lithium-assisted synergistic engineering of charge transport both in GBs and GI for Ag-substituted Cu2ZnSn(S,Se)4 solar cells

Although silver(Ag) substitution offers several benefits in eliminating bulk defects and facilitating interface type inversion for Cu2ZnSn(S,Se)4(CZTSSe) photovoltaic(PV) technology, its further development is still hindered by the fairly low electrical conductivity due to the significant decrease of acceptors amount.In this work, a versatile Li–Ag co-doping strategy is demonstrated to mitigate the poor electrical conductivity arising from Ag through direct incorporating Li via postdeposition treatment(PDT) on top of the Ag-substituted CZTSSe absorber. Depth characterizations demonstrate that Li incorporation increases ptype carrier concentration, improves the carrier collection within the bulk, reduces the defects energy level as well as inverts the electric field polarity at grain boundaries(GBs) for Ag-substituted CZTSSe system. Benefiting from this lithium-assisted complex engineering of electrical performance both in grain interior(GI) and GBs, the power conversion efficiency(PCE) is finally increased from 9.21% to 10.29%. This systematic study represents an effective way to overcome the challenges encountered in Ag substitution,and these findings support a new aspect that the synergistic effects of double cation dopant will further pave the way for the development of high efficiency kesterite PV technology.

Development of antimony sulfide–selenide Sb2(S,Se)3-based solar cells

Antimony sulfide–selenide Sb2（S,Se）3,including Sb2S3and Sb2Se3,can be regarded as binary metal chalcogenides semiconductors since Sb2S3and Sb2Se3are isomorphous.They possess abundant elemental storage,nontoxicity,good stability with regard to moisture at elevated temperatures and suitable physical parameters for light absorption materials in solar cells.To date,quite a few attempts have been conducted in the materials synthesis,photovoltaic property investigation and device fabrication.Benefiting from previous investigation in thin film solar cells and new generation nanostructured solar cells,this class of materials has been applied in either sensitized-architecture or planar heterojunction solar cells.Decent power conversion efficiencies from 5%to 7.5%have been achieved.Apparently,further improvement on the efficiency is required for future practical applications.To give an overview of this research field,this paper displays some typical researches regarding the methodologies toward the antimony sulfide–selenide synthesis,development of interfacial materials and device fabrications,during which we highlight some critical findings that promote the efficiency enhancement.Finally,this paper proposes some outstanding issue regarding fundamental understanding of the materials,some viewpoints for the efficiency improvement and their future challenges in solar cell applications.

First-principles study on the alkali chalcogenide secondary compounds in Cu(In,Ga)Se_2 and Cu_2ZnSn(S,Se)_4 thin film solar cells

The beneficial effect of the alkali metals such as Na and K on the Cu（In.Ga）Se2 （CIGS） and Cu2ZnSn（S,Se）4 （CZTSSe） solar cells has been extensively investigated in the past two decades, however, in most of the studies the alkali metals were treated as dopants. Several recent studies have showed that the alkali metals may not only act as dopants but also form secondary phases in the absorber layer or on the surfaces of the films. Using the first-principles calculations, we screened out the most probable secondary phases of Na and K in CIGS and CZTSSe, and studied their electronic structures and optical properties. We found that all these alkali chalcogenide compounds have larger band gaps and lower VBM levels than CIGS and CZTSSe, because the existence of strong p-d coupling in CIS and CZTS pushes the valence band maximum （VBM） level up and reduces the band-gaps, while there is no such p-d coupling in these alkali chalcogenides. This band alignment repels the photo-generated holes from the secondary phases and prevents the electron-hole recombination. Moreover, the study on the optical properties of the secondary phases showed that the absorption coefficients of these alkali chalcogenides are much lower than those of CIGS and CZTSSe in the energy range of 0-3.4eV, which means that the alkali chalcogenides may not influence the absorption of solar light. Since the alkali metal dopants can passivate the grain boundaries and increase the hole carrier concentration, and meanwhile their related secondary phases have innocuous effect on the optical absorption and band alignment, we can understand why the alkali metal dopants can improve the CIGS and CZTSSe solar cell performance.

Na-doping-induced modification of the Cu_(2)ZnSn(S,Se)_(4)/CdS heterojunction towards efficient solar cells

It is very important to understand why a small amount of alkali metal doping in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells can improve the conversion efficiency.In this work,Na-doped CZTSSe is prepared by a simple solution method,and then the effects on the surface properties of the absorber layer,the buffer layer growth,and the modifications of the solar cell performance induced by the Na doping are studied.The surface of the absorber layer is more Cu-depletion and less roughness due to the Na doping.In addition,the contact angle of the surface increases because of Na doping.As a consequence,the thickness of the CdS buffer layer is significantly reduced and the optical losses in the CdS buffer layer are decreased.The difference of quasi-Fermi levels(EFn-EFp) increases with a small amount of Na doping in the CZTSSe solar cell,so that open circuit voltage(VOC) increased significantly.This work offers new insights into the effects of Na doping on CZTSSe via a solution-based approach and provides a deeper understanding of the origin of the efficiency improvement of Na-doped CZTSSe thin film solar cells.

Review on Alkali Element Doping in Cu（In,Ga）Se2 Thin Films and Solar Cells

This paper reviews the development history of alkali element doping on Cu（In,Ga）Se2 （CIGS） solar cells and summarizes important achievements that have been made in this field. The influences of incorporation strategies on CIG5 absorbers and device performances are also reviewed. By analyzing CIGS surface structure and electronic property variation induced by alkali fluoride （NaF and KF） post-deposition treatment （PDT）, we discuss and interpret the following issues： ① The delamination of CIGS thin films induced by Na incorporation facilitates CulnSe2 formation and inhibits Ga during low-temperature co-evaporation process- es. ② The mechanisms of carrier density increase due to defect passivation by Na at grain boundaries and the surface. ③ A thinner buffer layer improves the short-circuit current without open-circuit voltage loss, This is attributed not only to better buffer layer coverage in the early stage of the chemical bath deposition process, but also to higher donor defect （Cd^＋Cu） density, which is transferred from the acceptor defect （C^-cu） and strengthens the buried homojunction. ④ The KF-PDT-induced lower valence band maximum at the absorber surface reduces the recombination at the absorber/buffer interface, which improves the open-circuit voltage and the fill factor of solar cells.

Numerical Modeling and Simulation of CIGS-Based Solar Cells with ZnS Buffer Layer

Usually a buffer layer of cadmium sulphide is used in high efficiency solar cells based on Cu(In,Ga)Se2(CIGS). Because of cadmium toxicity, many in-vestigations have been conducted to use Cd-free buffer layers. Our work focuses on this type of CIGS-based solar cells where CdS is replaced by a ZnS buffer layer. In this contribution, AFORS-HET software is used to simulate n-ZnO: Al/i-ZnO/n-ZnS/p-CIGS/Mo polycrystalline thin-film solar cell where the key parts are p-CIGS absorber layer and n-ZnS buffer layer. The characteristics of these key parts: thickness and Ga-content of the absorber layer, thickness of the buffer layer and doping concentrations of absorber and buffer layers have been investigated to optimize the conversion efficiency. We find a maximum conversion efficiency of 26% with a short-circuit current of 36.9 mA/cm2, an open circuit voltage of 824 mV, and a fill factor of 85.5%.

Texture engineering of mono-crystalline silicon via alcohol-free alkali solution for efficient PERC solar cells

Control of texture structures is an effective method to reduce surface reflectivity and enhance the efficiency of solar cells.In this paper,pyramid structures are prepared on mono-crystalline silicon wafers by cyclodextrin as surfactant to slow down the etching rate in alcohol-free alkali solution.Compared with volatile alcohol surfactant(e.g.isopropanol,IPA),the cyclodextrin not only possesses a relative high boiling point(1534.4℃),but displays non-toxic and biodegradable properties.Furthermore,the surface morphology,average reflectivity,surface recombination of mono-crystalline silicon wafers were studied in detail.The results show that cyclodextrin can decrease the size and depth of pyramid structures,and thus a lower average reflectivity of 7.5%was obtained.In addition,ray tracing simulation was performed to calculate the photo-generated carrier concentration of PN junction with different sizes of pyramids,and the conclusion is that the carrier concentration of small pyramids is much higher than that of large pyramids.Finally,the average efficiency of large-area mono-crystalline silicon PERC solar cells fabricated by cyclodextrin surfactant was 22.69%,which was 0.43%absolutely higher than that of conventional IPA surfactant.

Performance improvement of CdS/Cu(In,Ga)Se_2 solar cells after rapid thermal annealing

In this paper, we investigated the effect of rapid thermal annealing （RTA） on solar cell performance. An opto-electric conversion efficiency of 11.75% （Voc = 0.64 V, Jsc = 25.88 mA/cm2, FF=72.08%） was obtained under AM 1.5G when the cell was annealed at 300℃ for 30 s. The annealed solar cell showed an average absolute efficiency 1.5% higher than that of the as-deposited one. For the microstructure analysis and the physical phase confirmation, X-ray diffraction （XRD）, Raman spectra, front surface reflection （FSR）, internal quantum efficiency （IQE）, and X-ray photoelectron spectroscopy （XPS） were respectively applied to distinguish the causes inducing the efficiency variation. All experimental results implied that the RTA eliminated recombination centers at the p-n junction, reduced the surface optical losses, enhanced the blue response of the CdS buffer layer, and improved the ohmic contact between Mo and Cu（In, Ga）Se2 （CIGS） layers. This leaded to the improved performance of CIGS solar cell.

“SE+PERC”单晶硅太阳电池发射极方阻均匀性提升工艺的研究

针对“SE+PERC”单晶硅太阳电池制备过程中,管式扩散炉扩散后硅片发射极方阻均匀性差的问题,在扩散工艺的“预沉积”步骤设计小氮气(N_(2))流量、氧气(O_(2))流量、炉内压强参数变化实验,研究小N_(2)流量、O_(2)流量和炉内压强变化对发射极方阻、方阻均匀性及太阳电池电性能的影响。研究结果表明:通过调整小N_(2)流量、O_(2)流量及扩散过程中的炉内压强可以有效提高发射极方阻均匀性,并提高太阳电池的光电转换效率。在小N_(2)流量为1000 sccm、O_(2)流量为600 sccm、炉内压强为80 kPa的工艺条件下可实现发射极的方阻均匀性最佳,均值为4.94%;此时“SE+PERC”单晶硅太阳电池的光电转换效率为23.11%。

链式热氧化与槽式碱抛光工艺条件对PERC单晶硅太阳电池光电转换效率的影响

针对PERC单晶硅太阳电池制备工艺中3合1工序的链式热氧化工艺的氧化性能与槽式碱抛光工艺酸洗槽的去氧化能力的工艺窗口及匹配性进行了研究。首先设计实验分别测试链式热氧化工艺条件(包括温度、氧气流量)、槽式碱抛光工艺的酸洗槽液体浓度对扩散后硅片表面掺杂浓度及PERC单晶硅太阳电池光电转换效率的影响;再根据初步实验结果对链式热氧化工艺与槽式碱抛光工艺的匹配性进行分析,得到整体3合1工序的优化工艺方案;然后采用电化学微分电容电压(ECV)测试扩散后硅片表面掺杂浓度及结深的变化情况,对研究结果进行了佐证,最终达到提升PERC单晶硅太阳电池光电转换效率的目的。研究结果表明:3合1工序中的链式热氧化工艺与槽式碱抛光工艺对扩散后硅片表面掺杂浓度及PERC单晶硅太阳电池电性能存在重要影响,优化链式热氧化工艺的温度、氧气流量与槽式碱抛光工艺的酸洗槽液体浓度,提高二者的匹配性,使氧化能力与去氧化能力均达到临界点,可以最大程度地提高PERC单晶硅太阳电池的光电转换效率。

硅片表面织构对“SE+PERC”双面单晶硅太阳电池电性能影响的研究

在硅片制绒过程,研究了制绒添加剂体积分数、反应时间和反应温度对单晶硅片表面织构的微观形貌、反射率,以及制备的“选择性发射极(SE)+PERC”双面单晶硅太阳电池电性能的影响。结果表明:在目前单晶硅片制绒设备和工艺条件下,当碱液(KOH)体积分数为2%、制绒添加剂体积分数为0.7%、反应温度为84℃、反应时间为440 s时,制备的单晶硅片表面的金字塔尺寸较小,均匀性强,硅片表面的反射率最低,仅为9.914%,而得到的“SE+PERC”双面单晶硅太阳电池的光电转换效率高达22.714%;调整制绒参数,可以有效提高单晶硅片表面织构中金字塔的均匀性,降低硅片表面的反射率,从而提高“SE+PERC”双面单晶硅太阳电池的光电转换效率。

“SE+PERC”单晶硅太阳电池激光掺杂区域的漏电现象研究

在选择性发射极(SE)技术与钝化发射极背接触(PERC)技术相结合(即“SE+PERC”)的单晶硅太阳电池技术路线中,通常采用激光技术进行局部重掺杂,即利用激光的高温特性将硅片表面磷硅玻璃(PSG)层内的磷原子推入硅片内部,形成高低结,从而提高太阳电池的光电转换效率。但是经过激光扫描后的掺杂区域表面的PSG层会被激光损伤,损伤区域在进行碱抛光时常因掩膜的保护性差而被碱溶液腐蚀,导致p-n结被破坏,造成局部严重漏电,从而影响太阳电池的整体电性能。针对“SE+PERC”单晶硅太阳电池制备过程中激光掺杂区域出现的漏电现象,分析了漏电原因,并给出了采用SE激光掺杂工艺及碱抛光工艺时的优化建议。

SE+PERC太阳电池扩散工艺的研究

近年来晶体硅太阳电池PERC技术已经全面推广,在此基础上的选择性发射极(selective emiter,SE)激光掺杂技术也逐渐趋于成熟,已实现工业化量产,且以产线升级简单、兼容性好等优势逐渐成为新一代主流产品。论述了一种匹配SE+PERC技术的新型太阳电池扩散工艺,即通过改善磷硅玻璃(PSG)层的厚度、表面掺杂浓度来降低激光掺杂过程对硅片绒面的损伤,从而减少开路电压的损失;同时重掺区得到更高的掺杂浓度,可以明显改善欧姆接触,使SE激光掺杂技术的优势体现得更明显。

基于激光掺杂的SE+PERC单晶硅太阳电池关键工艺的研究

在现阶段主流太阳电池生产设备的水平条件下,研究了激光频率、初始方块电阻和烧结峰值温度对基于激光掺杂的选择性发射极(SE)+PERC单晶硅太阳电池电性能的影响。分别采用奥林巴斯显微镜和Halm电学性能测试仪,分析了不同频率的激光在硅片表面形成的光斑形貌,以及不同实验条件时电池的电性能变化趋势。结果表明,激光频率为220 kHz时有利于在硅片表面形成连续性且不重叠的光斑,形成最佳重掺杂区,从而提升电池转换效率;基于现有的常压扩散设备的掺杂水平,在确保硅片表面方块电阻均匀性的情况下,初始方块电阻选择120Ω/□更有利于提升电池的转换效率;烧结峰值温度为790℃时,更有利于在电池电极位置形成良好的欧姆接触,从而获得最佳的电池转换效率。