CN103343318A - Preparation method of light absorption layer of solar battery - Google Patents
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Abstract
本发明涉及一种太阳能电池的光吸收层的制备方法,包括制备金属薄膜前驱体,金属薄膜前驱体为铜锌锡硫前驱体薄膜或铜锌锡硒前驱体薄膜;制备层叠于金属薄膜前驱体上的锡覆盖层,得到层叠有锡覆盖层的铜锌锡硫薄膜前驱体或层叠有锡覆盖层的铜锌锡硒薄膜前驱体;及在无氧条件下及硫化氢气氛中,将层叠有锡覆盖层的铜锌锡硫薄膜前驱体进行高温退火;或者在无氧条件下及硒气氛中,将层叠有锡覆盖层的铜锌锡硒薄膜前驱体进行高温退火,得到太阳能电池的光吸收层的步骤。锡覆盖层能够阻止在高温退火中金属薄膜前驱体内SnS2或SnSe2的挥发,退火后,锡覆盖层中的Sn形成SnS2或SnSe2并脱离晶体,有效抑制Sn的流失。
The invention relates to a method for preparing a light-absorbing layer of a solar cell, comprising preparing a metal film precursor, the metal film precursor being a copper-zinc-tin-sulfur precursor film or a copper-zinc-tin-selenium precursor film; preparing a film laminated on the metal film precursor The tin covering layer on the upper layer is obtained to be stacked with a copper zinc tin sulfur film precursor of a tin covering layer or a copper zinc tin selenium film precursor being laminated with a tin covering layer; and under an oxygen-free condition and in a hydrogen sulfide atmosphere, the stacked The copper-zinc-tin-sulfur film precursor of the tin coating layer is subjected to high-temperature annealing; or under oxygen-free conditions and in a selenium atmosphere, the copper-zinc-tin-selenium thin film precursor laminated with the tin coating layer is subjected to high-temperature annealing to obtain the light absorption of the solar cell. layer steps. The tin capping layer can prevent the volatilization of SnS 2 or SnSe 2 in the metal film precursor during high temperature annealing. After annealing, the Sn in the tin capping layer forms SnS 2 or SnSe 2 and breaks away from the crystal, effectively inhibiting the loss of Sn.
Description
技术领域technical field
本发明涉及光伏器件制备技术领域,特别是涉及一种太阳能电池的光吸收层的制备方法。The invention relates to the technical field of photovoltaic device preparation, in particular to a method for preparing a light absorbing layer of a solar cell.
背景技术Background technique
具有锌黄锡矿结构的CZTS(铜锌锡硫,Cu2ZnSnS4)与CZTSe(铜锌锡硒,Cu2ZnSnSe4)的禁带宽度与半导体太阳电池的最佳禁带宽度1.5eV十分接近,其吸收系数可达到104cm-1。铜锌锡硫硒中的元素铜、锌、锡、硫和硒在地球上的储量非常丰富,价格便宜,并且都是环境友好元素,不含有毒成分,已经成为当今光伏领域研究的热点领域,有可能成为未来光伏电池的主流产品。The band gap of CZTS (copper zinc tin sulfur, Cu 2 ZnSnS 4 ) and CZTSe (copper zinc tin selenium, Cu 2 ZnSnSe 4 ) with kesterite structure is very close to the optimal band gap of 1.5eV for semiconductor solar cells , its absorption coefficient can reach 10 4 cm -1 . The elements copper, zinc, tin, sulfur, and selenium in copper, zinc, tin, sulfur, and selenium are very abundant on the earth, cheap, and all are environmentally friendly elements without toxic components. They have become a hot research field in the field of photovoltaics today. It is possible to become the mainstream product of photovoltaic cells in the future.
CZTS薄膜太阳能电池及CZTSe薄膜太阳能电池的主要制备工艺路线是在低温条件下利用磁控溅射、共蒸发、电沉积、溶液法等方法制备出金属前躯体薄膜,然后高温退火,即将该金属薄膜前驱体置于高温状态下,使金属薄膜前躯体内的原子发生化学反应、反应生成物结晶,得到多晶态的CZTS薄膜或CZTSe薄膜,即太阳能电池的光吸收层。退火之后的CZTS薄膜或CZTSe薄膜经过水浴法沉积硫化镉(CdS)、铝掺杂的氧化锌(AZO)薄膜生长、电子束蒸发制作Ni-Al电极,即为薄膜太阳能电池器件。The main preparation process route of CZTS thin-film solar cells and CZTSe thin-film solar cells is to prepare metal precursor thin films by magnetron sputtering, co-evaporation, electrodeposition, solution method and other methods under low temperature conditions, and then anneal at high temperature to form the metal thin films. The precursor is placed in a high-temperature state, so that the atoms in the metal film precursor undergo a chemical reaction, and the reaction product crystallizes to obtain a polycrystalline CZTS film or CZTSe film, which is the light-absorbing layer of the solar cell. After annealing, the CZTS film or CZTSe film is deposited by water bath method to deposit cadmium sulfide (CdS), aluminum-doped zinc oxide (AZO) film growth, and electron beam evaporation to make Ni-Al electrode, which is a thin film solar cell device.
所谓高温退火过程,是将金属薄膜前驱体在真空中快速升温并保持温度一段时间后,再自然降温的过程。The so-called high-temperature annealing process is a process in which the metal film precursor is rapidly heated up in vacuum and maintained at the temperature for a period of time, and then naturally cooled.
以CZTS金属薄膜前驱体为例,CZTS金属薄膜前躯体高温退火过程逐步发生如下反应:Taking the CZTS metal thin film precursor as an example, the following reactions gradually occur during the high-temperature annealing process of the CZTS metal thin film precursor:
第一阶段,生成二元相:In the first stage, a binary phase is generated:
Cu+S→Cu2S;Cu+S→ Cu2S ;
第二阶段,二元相反应生成三元相:In the second stage, the binary phase reacts to form the ternary phase:
Cu2S+SnS2→Cu2SnS3; Cu2S + SnS2 → Cu2SnS3 ;
第三阶段,生成四元相:In the third stage, the quaternary phase is generated:
Cu2SnS3+ZnS→Cu2ZnSnS4。Cu 2 SnS 3 +ZnS→Cu 2 ZnSnS 4 .
最近对二元相的研究发现,Sn和S两种元素在300℃开始形成SnS2,在400℃时开始大量挥发,460℃时该二元相不再以固态存在,而这个温度远低于CZTS所需要的结晶温度。对四元相CZTS薄膜前驱体退火前后薄膜前躯体和晶态薄膜的组分变化通过EDS能谱分析表明,CZTS薄膜前躯体完成退火之后Sn的流失量可高达24%,且Sn元素的流失的现象不仅存在于薄膜表面,还存在于整个薄膜层内部。因此,CZTS薄膜在达到反应温度之前,Sn元素会随着SnS2的挥发大量流失。造成的后果是,CZTS薄膜组分中Sn组分的量不易控制,影响了CZTS薄膜层的质量。Recent studies on binary phases have found that Sn and S two elements begin to form SnS 2 at 300°C, and begin to volatilize in large quantities at 400°C, and the binary phase no longer exists in solid state at 460°C, which is much lower than Crystallization temperature required for CZTS. The EDS energy spectrum analysis of the composition changes of the film precursor and crystalline film before and after the annealing of the quaternary phase CZTS film precursor shows that the loss of Sn after the annealing of the CZTS film precursor can be as high as 24%, and the loss of Sn element The phenomenon exists not only on the surface of the film, but also inside the entire film layer. Therefore, before the CZTS film reaches the reaction temperature, the Sn element will lose a large amount with the volatilization of SnS2 . The consequence is that the amount of Sn component in the CZTS thin film component is not easy to control, which affects the quality of the CZTS thin film layer.
CZTSe与CZTS的性质相似,Se与S两种元素属于同族元素,其二元相SnSe2和SnS2的性质也相似,可与上述原理类比,CZTSe金属薄膜前躯体高温退火过程,由于SnSe2的挥发而导致Sn大量流失,造成CZTSe薄膜组分的偏差,从而影响了CZTSe薄膜层的质量。The properties of CZTSe and CZTS are similar. Se and S belong to the same group of elements, and the properties of the binary phases SnSe 2 and SnS 2 are also similar. It can be compared with the above principle. During the high-temperature annealing process of the CZTSe metal film precursor, due to the The volatilization causes a large loss of Sn, which causes the deviation of the composition of the CZTSe film, thus affecting the quality of the CZTSe film layer.
发明内容Contents of the invention
基于此,有必要提供一种能够抑制Sn流失的太阳能电池的光吸收层的制备方法。Based on this, it is necessary to provide a method for preparing a light absorbing layer of a solar cell capable of suppressing Sn loss.
一种太阳能电池的光吸收层的制备方法,包括如下步骤:A method for preparing a light absorbing layer of a solar cell, comprising the steps of:
制备金属薄膜前驱体,所述金属薄膜前驱体为铜锌锡硫薄膜前驱体或铜锌锡硒薄膜前驱体;preparing a metal thin film precursor, the metal thin film precursor being a copper zinc tin sulfur thin film precursor or a copper zinc tin selenium thin film precursor;
制备层叠于所述金属薄膜前驱体上的锡覆盖层,得到层叠有锡覆盖层的金属薄膜前驱体,所述层叠有锡覆盖层的金属薄膜前驱体为层叠有锡覆盖层的铜锌锡硫薄膜前驱体或层叠有锡覆盖层的铜锌锡硒薄膜前驱体;及Prepare the tin covering layer laminated on the metal thin film precursor to obtain the metal thin film precursor laminated with the tin covering layer, the metal thin film precursor laminated with the tin covering layer is copper zinc tin sulfur laminated with the tin covering layer A thin film precursor or a CuZnTnSe thin film precursor laminated with a tin capping layer; and
在无氧条件下及硫化氢气氛中,将所述层叠有锡覆盖层的铜锌锡硫薄膜前驱体进行高温退火;或者在无氧条件下及硒气氛中,将所述层叠有锡覆盖层的铜锌锡硒薄膜前驱体进行高温退火,得到太阳能电池的光吸收层。Under oxygen-free conditions and in a hydrogen sulfide atmosphere, the copper-zinc-tin-sulfur film precursor laminated with a tin coating layer is subjected to high-temperature annealing; or under an oxygen-free condition and in a selenium atmosphere, the stacked tin coating layer is The copper-zinc-tin-selenium film precursor is annealed at high temperature to obtain the light absorption layer of the solar cell.
在其中一个实施例中,所述制备金属薄膜前驱体的步骤是采用共溅射法或共蒸发法制备金属薄膜前驱体。In one of the embodiments, the step of preparing the metal thin film precursor is to prepare the metal thin film precursor by co-sputtering or co-evaporation.
在其中一个实施例中,所述制备金属薄膜前驱体的步骤是采用共溅射法将铜、硫化锌和二硫化锡溅射至衬底上,形成层叠于所述衬底上的铜锌锡硫薄膜前驱体;或采用共溅射法将铜、硒化锌和二硒化锡溅射至衬底上,形成层叠于所述衬底上的铜锌锡硒薄膜前驱体。In one of the embodiments, the step of preparing the metal thin film precursor is to sputter copper, zinc sulfide and tin disulfide onto the substrate by a co-sputtering method to form a copper-zinc-tin layer stacked on the substrate. Sulfur thin film precursor; or co-sputtering copper, zinc selenide and tin diselenide onto the substrate to form a copper zinc tin selenide thin film precursor stacked on the substrate.
在其中一个实施例中,所述制备金属薄膜前驱体的步骤是采用共蒸发法将铜、硫化锌、锡和硫蒸发沉积至衬底上,形成层叠于所述衬底上的铜锌锡硫薄膜前驱体;或采用共蒸发法将铜、硒化锌、锡和硒蒸发沉积至衬底上,形成层叠于所述衬底上的铜锌锡硒薄膜前驱体。In one of the embodiments, the step of preparing the metal thin film precursor is to vapor-deposit copper, zinc sulfide, tin and sulfur onto the substrate by co-evaporation to form a copper-zinc-tin-sulfur layer stacked on the substrate. A thin film precursor; or co-evaporating copper, zinc selenide, tin and selenium onto a substrate to form a copper zinc tin selenium thin film precursor stacked on the substrate.
在其中一个实施例中,所述采用共溅射法制备金属薄膜前驱体之前还包括预溅射的步骤。In one of the embodiments, the step of pre-sputtering is also included before the preparation of the metal film precursor by the co-sputtering method.
在其中一个实施例中,所述制备层叠于所述金属薄膜前驱体上的锡覆盖层的步骤是采用磁控溅射或热蒸发将元素锡沉积在所述金属薄膜前驱体上,得到层叠有锡覆盖层的金属薄膜前驱体。In one of the embodiments, the step of preparing the tin covering layer laminated on the metal film precursor is to deposit elemental tin on the metal film precursor by using magnetron sputtering or thermal evaporation to obtain a layered Precursors for thin metal films with tin overlays.
在其中一个实施例中,所述锡覆盖层的厚度为150纳米。In one embodiment, the thickness of the tin capping layer is 150 nanometers.
在其中一个实施例中,所述高温退火的温度为550℃,时间为15分钟。In one embodiment, the temperature of the high temperature annealing is 550° C., and the time is 15 minutes.
在其中一个实施例中,所述硫化氢的气压为2×103Pa。In one embodiment, the pressure of the hydrogen sulfide is 2×10 3 Pa.
在其中一个实施例中,所述在无氧条件下及硫化氢气氛中,将所述层叠有锡覆盖层的铜锌锡硫薄膜前驱体进行高温退火的步骤具体为:将所述层叠有锡覆盖层的铜锌锡硫薄膜前驱体放置于退火炉中,通入硫化氢至气压为2×103Pa,再通入氮气至气压为4×104Pa,然后加热所述层叠有锡覆盖层的铜锌锡硫薄膜前驱体至550℃,保温15分钟后自然冷却;所述在无氧条件下及硒气氛中,将所述层叠有锡覆盖层的铜锌锡硒薄膜前驱体进行高温退火的步骤具体为:将所述层叠有锡覆盖层的铜锌锡硒薄膜前驱体放置于退火炉中,通入硫化硒至气压为2×103Pa,再通入氮气至气压为4×104Pa,然后加热所述层叠有锡覆盖层的铜锌锡硒薄膜前驱体至550℃,保温15分钟后自然冷却。In one of the embodiments, the step of performing high-temperature annealing on the copper-zinc-tin-sulfur thin film precursor laminated with a tin coating layer under oxygen-free conditions and in a hydrogen sulfide atmosphere is specifically: The copper-zinc-tin-sulfur film precursor of the covering layer is placed in an annealing furnace, and hydrogen sulfide is introduced to a pressure of 2×10 3 Pa, and then nitrogen is introduced to a pressure of 4×10 4 Pa. layered copper zinc tin sulfur thin film precursor to 550 ℃, naturally cooled after 15 minutes of heat preservation; described under anaerobic conditions and in a selenium atmosphere, the copper zinc tin selenium thin film precursor stacked with a tin coating layer is subjected to high temperature The annealing step is specifically as follows: placing the copper-zinc-tin-selenide thin film precursor laminated with a tin coating layer in an annealing furnace, feeding selenium sulfide to a pressure of 2×10 3 Pa, and then feeding nitrogen gas to a pressure of 4× 10 4 Pa, and then heat the copper-zinc-tin-selenide thin film precursor laminated with a tin covering layer to 550° C., keep it warm for 15 minutes, and then cool it down naturally.
上述太阳能电池的光吸收层的制备方法,在金属薄膜前驱体的表面形成锡覆盖层,利用锡覆盖层阻止在高温退火过程中,铜锌锡硫薄膜前驱体内SnS2的挥发或铜锌锡硒薄膜前驱体内SnSe2的挥发,从而达到抑制金属薄膜前驱体内Sn元素流失的目的,铜锌锡硫薄膜前驱体或铜锌锡硒薄膜前驱体经过退火形成致密的CZTS晶体或CZTSe晶体后,表面锡覆盖层中的Sn在硫化氢气氛下逐渐形成SnS2并脱离CZTS晶体表面,或在硫化硒气氛下形成SnSe2并脱离CZTSe晶体表面,这个过程不会影响到CZTS晶体或CZTSe晶体的组分,避免了SnS2或SnSe2的挥发而导致Sn的流失,从而制备得到质量较高的CZTS光吸收层或CZTSe光吸收层。The preparation method of the light-absorbing layer of the above-mentioned solar cell forms a tin covering layer on the surface of the metal thin film precursor, and utilizes the tin covering layer to stop in the high-temperature annealing process, the volatilization of SnS in the copper-zinc-tin- sulfur film precursor or the copper-zinc-tin-selenide The volatilization of SnSe 2 in the thin film precursor can achieve the purpose of inhibiting the loss of Sn element in the metal thin film precursor. The Sn in the capping layer gradually forms SnS2 and detaches from the CZTS crystal surface under the hydrogen sulfide atmosphere, or forms SnSe2 and detaches from the CZTSe crystal surface under the selenium sulfide atmosphere, this process will not affect the composition of the CZTS crystal or the CZTSe crystal, The loss of Sn caused by the volatilization of SnS2 or SnSe2 is avoided, so that a higher-quality CZTS light-absorbing layer or CZTSe light-absorbing layer is prepared.
附图说明Description of drawings
图1为一实施方式的太阳能电池的光吸收层的制备方法的流程图;Fig. 1 is the flowchart of the preparation method of the light absorbing layer of the solar cell of one embodiment;
图2为图1所示的太阳能电池的光吸收层的制备方法的步骤S110的示意图。FIG. 2 is a schematic diagram of step S110 of the method for preparing the light absorbing layer of the solar cell shown in FIG. 1 .
具体实施方式Detailed ways
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似改进,因此本发明不受下面公开的具体实施的限制。In order to make the above objects, features and advantages of the present invention more comprehensible, specific implementations of the present invention will be described in detail below in conjunction with the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, the present invention can be implemented in many other ways different from those described here, and those skilled in the art can make similar improvements without departing from the connotation of the present invention, so the present invention is not limited by the specific implementations disclosed below.
请参阅图1,一实施方式的太阳能电池的光吸收层的制备方法,包括下述步骤S110至步骤S130。Please refer to FIG. 1 , a method for preparing a light absorbing layer of a solar cell according to an embodiment includes the following steps S110 to S130 .
步骤S110:制备金属薄膜前驱体。Step S110: preparing a metal thin film precursor.
金属薄膜前驱体为铜锌锡硫(CZTS)薄膜前驱体或铜锌锡硒(CZTSe)薄膜前驱体。The metal thin film precursor is a copper zinc tin sulfur (CZTS) thin film precursor or a copper zinc tin selenium (CZTSe) thin film precursor.
请同时参阅图2,首先提供衬底。衬底为玻璃衬底,将衬底清洗干净并干燥后,在洁净、干燥的衬底上沉积钼形成层叠于衬底上的钼背电极层,得到层叠有钼背电极层的衬底101。优选地,钼背电极层的厚度为800纳米或150纳米。Please also refer to Figure 2, first provide the substrate. The substrate is a glass substrate. After the substrate is cleaned and dried, molybdenum is deposited on the clean and dry substrate to form a molybdenum back electrode layer laminated on the substrate to obtain a
以金属薄膜前驱体为铜锌锡硫(CZTS)薄膜前驱体为例,采用共溅射法共同溅射铜(Cu)、硫化锌(ZnS)和二硫化锡(SnS2),将铜、硫化锌和二硫化锡溅射至钼背电极层上。制备过程具体如下:Taking the copper zinc tin sulfur (CZTS) film precursor as the metal film precursor as an example, copper (Cu), zinc sulfide (ZnS) and tin Zinc and tin disulfide were sputtered onto the molybdenum back electrode layer. The preparation process is as follows:
将层叠有钼背电极层的衬底101放入溅射设备的溅射腔室的样品架上。层叠有钼背电极层的衬底101的钼背电极层朝向衬底挡板102。The
对溅射腔室进行抽真空,首先用机械泵抽真空至电阻规读数为5×101Pa然后开启分子泵抽真空至电离规读数为2×10-3Pa。打开气体流量计,向溅射腔室内以12sccm的流量通入99.999%的高纯氩气,控制真空系统使电离规读数维持在1.1×10-1Pa。样品架旋转,打开各个靶(Cu靶、ZnS靶、SnS2靶和Sn靶)的射频溅射电源,调整电源输出功率及反射功率,使靶材起辉。预溅射10分钟后,开启各靶挡板(Cu靶挡板103、ZnS靶挡板104和SnS2靶挡板105)、衬底挡板102以及膜厚仪挡板(图未示)。通过膜厚仪检测溅射速率。溅射1小时后,关闭Cu靶挡板103、ZnS靶挡板104和SnS2靶挡板105,形成层叠于衬底的钼背电极层上的铜锌锡硫薄膜前驱体。To evacuate the sputtering chamber, first use a mechanical pump to evacuate until the reading of the resistance gauge is 5×10 1 Pa, then turn on the molecular pump to evacuate until the reading of the ionization gauge is 2×10 -3 Pa. Turn on the gas flow meter, feed 99.999% high-purity argon gas into the sputtering chamber at a flow rate of 12 sccm, and control the vacuum system to maintain the reading of the ionization gauge at 1.1×10 -1 Pa. Rotate the sample holder, turn on the RF sputtering power supply of each target (Cu target, ZnS target, SnS 2 target and Sn target), adjust the output power and reflection power of the power supply, and make the target glow. After 10 minutes of pre-sputtering, each target shutter (
优选地,铜锌锡硫薄膜前驱体的厚度为1.3微米~1.7微米。Preferably, the thickness of the copper-zinc-tin-sulfur thin film precursor is 1.3 microns to 1.7 microns.
优选地,Cu靶的功率为60W、ZnS靶的功率为75W、SnS2靶的功率为70W。Preferably, the power of the Cu target is 60W, the power of the ZnS target is 75W, and the power of the SnS2 target is 70W.
预溅射是指,打开各个靶(Cu靶、ZnS靶、SnS2靶和Sn靶)的射频溅射电源,调整电源输出功率及反射功率,使靶材起辉,但此时不打开Cu靶挡板103、ZnS靶挡板104、SnS2靶挡板105、Sn靶挡板106及衬底挡板102,以将各个靶材表面上的杂质除去。优选地,预溅射的时间为10分钟,以保证将各个靶材上的杂质充分除去后再打开Cu靶挡板103、ZnS靶挡板104、SnS2靶挡板105及衬底挡板102进行前驱体的制备,将铜、硫化锌和二硫化锡溅射至钼背电极层上,溅射至钼背电极层上的铜、硫化锌和二硫化锡形成无杂质的铜锌锡硫前驱体薄膜。Pre-sputtering refers to turning on the RF sputtering power supply of each target (Cu target, ZnS target, SnS 2 target and Sn target), adjusting the power output power and reflected power to make the target glow, but not turning on the Cu target at this time The
当金属薄膜前驱体为铜锌锡硒薄膜前驱体时,采用共溅射制备该铜锌锡硒薄膜前驱体的方法与上述制备铜锌锡硫薄膜前驱体的方法大致相同,不同的是靶材替换为Cu靶、ZnSe靶、SnSe2靶。预溅射10分钟后,开启各靶挡板(Cu靶挡板、ZnSe靶挡板、SnSe2靶挡板)、衬底挡板以及膜厚仪挡板。通过膜厚仪检测溅射速率。溅射1小时后,关闭Cu靶挡板、ZnSe靶挡板和SnSe2靶挡板,形成层叠于衬底的背电极层上的铜锌锡硒薄膜前驱体。优选地,Cu靶的功率为60W、ZnSe靶的功率为75W、SnSe2靶的功率为70W。When the metal thin film precursor is a copper zinc tin selenium thin film precursor, the method for preparing the copper zinc tin selenium thin film precursor by co-sputtering is roughly the same as the above method for preparing the copper zinc tin sulfur thin film precursor, the difference is that the target Replace with Cu target, ZnSe target, SnSe 2 target. After 10 minutes of pre-sputtering, each target shutter (Cu target shutter, ZnSe target shutter, SnSe2 target shutter), substrate shutter and film thickness meter shutter were opened. The sputtering rate was detected by a film thickness meter. After sputtering for 1 hour, close the Cu target shutter, the ZnSe target shutter and the SnSe 2 target shutter to form a copper zinc tin selenium thin film precursor stacked on the back electrode layer of the substrate. Preferably, the power of the Cu target is 60W, the power of the ZnSe target is 75W, and the power of the SnSe2 target is 70W.
优选地,铜锌锡硒薄膜前驱体的厚度为1.3微米~1.7微米。Preferably, the thickness of the copper zinc tin selenium thin film precursor is 1.3 microns to 1.7 microns.
在其他实施方式中,也可以采用共蒸发制备金属薄膜前驱体。将铜、硫化锌和二硫化锡共同蒸发沉积至衬底的钼背电极层上,形成层叠于钼背电极层上的铜锌锡硫薄膜前驱体;或者将铜、硒化锌、锡和硒共同蒸发沉积至衬底的钼背电极层上,形成层叠于钼背电极层上的铜锌锡硒薄膜前驱体。In other embodiments, co-evaporation can also be used to prepare the metal thin film precursor. Co-evaporative deposition of copper, zinc sulfide and tin disulfide onto the molybdenum back electrode layer of the substrate to form a copper zinc tin sulfur film precursor laminated on the molybdenum back electrode layer; or copper, zinc selenide, tin and selenium Co-evaporating and depositing on the molybdenum back electrode layer of the substrate to form a copper zinc tin selenium thin film precursor laminated on the molybdenum back electrode layer.
采用共蒸发制备金属薄膜前驱体在分子束外延系统(MBE系统)中进行。将层叠有钼背电极层的衬底101放入MBE腔体的样品台上,将Cu源炉、ZnS源炉、Sn源炉、S源炉及样品台分别加热至预设温度后,同时打开Cu源炉挡板、ZnS源炉挡板、Sn源炉挡板、S源炉挡板及样品台挡板,进行蒸镀得到铜锌锡硫薄膜前驱体。Co-evaporation is used to prepare metal thin film precursors in a molecular beam epitaxy system (MBE system). Put the
共蒸发法制备铜锌锡硫薄膜前驱体时,优选地,Cu源炉、ZnS源炉、Sn源炉、S源炉及样品台的预设温度分别为1210℃、765℃、1140℃、200℃及200℃。When the copper-zinc-tin-sulfur film precursor is prepared by the co-evaporation method, preferably, the preset temperatures of the Cu source furnace, the ZnS source furnace, the Sn source furnace, the S source furnace and the sample stage are 1210°C, 765°C, 1140°C, 200°C, respectively. ℃ and 200℃.
共蒸发法制备铜锌锡硒薄膜前驱体时,优选地,Cu源炉、ZnSe源炉、Sn源炉、Se源炉及样品台的预设温度分别为1210℃、765℃、1140℃、210℃及200℃。When the copper-zinc-tin-selenium film precursor is prepared by the co-evaporation method, preferably, the preset temperatures of the Cu source furnace, the ZnSe source furnace, the Sn source furnace, the Se source furnace and the sample stage are 1210°C, 765°C, 1140°C, 210°C, respectively. ℃ and 200℃.
步骤S120:制备层叠于金属薄膜前驱体上的锡覆盖层,得到层叠有锡覆盖层的金属薄膜前驱体。Step S120: preparing a tin capping layer stacked on the metal thin film precursor to obtain a metal thin film precursor stacked with a tin capping layer.
层叠有锡覆盖层的金属薄膜前驱体为层叠有锡覆盖层的铜锌锡硫薄膜前驱体或层叠有锡覆盖层的铜锌锡硒薄膜前驱体。The precursor of the metal film laminated with a tin covering layer is a precursor of a copper zinc tin sulfur film laminated with a tin covering layer or a precursor of a copper zinc tin selenium film laminated with a tin covering layer.
在衬底的钼背电极层上形成铜锌锡硫薄膜前驱体后,打开Sn靶挡板106,溅射10分钟后,关闭Sn靶挡板106,关闭各靶电源、膜厚仪、样品旋转及气体流量计,冷却30分钟后,在铜锌锡硫薄膜前驱体上形成锡覆盖层,得到层叠有锡覆盖层的铜锌锡硫薄膜前驱体。After the copper-zinc-tin-sulfur film precursor is formed on the molybdenum back electrode layer of the substrate, open the
或,在衬底的钼背电极层上形成铜锌锡硒薄膜前驱体后,打开Sn靶挡板,溅射10分钟后,关闭Sn靶挡板,关闭各靶电源、膜厚仪、样品旋转及气体流量计,冷却30分钟后,在铜锌锡硒薄膜前驱体上形成锡覆盖层,得到层叠有锡覆盖层的铜锌锡硒薄膜前驱体。Or, after the copper zinc tin selenium thin film precursor is formed on the molybdenum back electrode layer of the substrate, open the Sn target baffle, after sputtering for 10 minutes, close the Sn target baffle, turn off the power supply of each target, the film thickness meter, and the sample rotation and a gas flowmeter, after cooling for 30 minutes, a tin covering layer is formed on the copper zinc tin selenium thin film precursor to obtain a copper zinc tin selenium thin film precursor laminated with a tin covering layer.
优选地,Sn靶的功率为50W。Preferably, the power of the Sn target is 50W.
Sn的蒸汽压非常小,在1100℃时仅为10-4Pa,几乎可以认为是稳定不挥发的,因此,锡覆盖层很稳定,能够阻止铜锌锡硫前驱体薄膜内的SnS2挥发或阻止铜锌锡硒前驱体薄膜内的SnSe2挥发。The vapor pressure of Sn is very small, only 10 -4 Pa at 1100 °C, and it can be considered as stable and non-volatile. Therefore, the tin coating is very stable and can prevent the SnS 2 in the copper-zinc-tin-sulfur precursor film from volatilizing or Prevent the volatilization of SnSe2 in the copper zinc tin selenium precursor thin film.
锡覆盖层的厚度为100纳米~200纳米,优选为150纳米。锡覆盖层厚度的选择一方面要足够厚以抑制金属薄膜前驱体内部SnS2或者SnSe2的挥发,另一方面又不能太厚,以便后续步骤能全部除去。锡覆盖层的厚度为150纳米时能够较好地满足上述两个要求。The thickness of the tin covering layer is 100 nm to 200 nm, preferably 150 nm. The thickness of the tin coating should be thick enough to suppress the volatilization of SnS 2 or SnSe 2 inside the metal thin film precursor on the one hand, but not too thick so that it can be completely removed in subsequent steps. When the thickness of the tin covering layer is 150 nanometers, the above two requirements can be better satisfied.
在其他实施方式中,也可以采用热蒸发的方法将锡沉积在金属薄膜前驱体上制备层叠于金属薄膜前驱体上的锡覆盖层。采用热蒸发形成锡覆盖层时,Sn源炉的预设温度优选为1150℃。In other embodiments, tin can also be deposited on the metal thin film precursor by thermal evaporation to prepare a tin capping layer stacked on the metal thin film precursor. When thermal evaporation is used to form the tin coating layer, the preset temperature of the Sn source furnace is preferably 1150°C.
步骤S130:在无氧条件下及硫化氢气氛中,将层叠有锡覆盖层的铜锌锡硫薄膜前驱体进行高温退火;或者在无氧条件下及硒气氛中,将层叠有锡覆盖层的铜锌锡硒薄膜前驱体进行高温退火,得到太阳能电池的光吸收层。Step S130: Under an oxygen-free condition and a hydrogen sulfide atmosphere, perform high-temperature annealing on the copper-zinc-tin-sulfur thin film precursor laminated with a tin coating layer; or under an oxygen-free condition and in a selenium atmosphere, anneal the The copper-zinc-tin-selenide film precursor is annealed at high temperature to obtain the light absorption layer of the solar cell.
针对铜锌锡硫薄膜前驱体:For CuZnSnS thin film precursors:
将层叠有锡覆盖层的铜锌锡硫薄膜前驱体放入退火炉中,用机械泵从1×105Pa抽真空至薄膜真空规读数为0Pa。用计时器计时继续抽5分钟,以保证退火炉清洁。Put the copper-zinc-tin-sulfur thin film precursor laminated with a tin coating layer into an annealing furnace, and use a mechanical pump to evacuate from 1×10 5 Pa until the reading of the thin film vacuum gauge is 0 Pa. Continue pumping for 5 minutes with a timer to ensure that the annealing furnace is clean.
关闭机械泵角阀,先向退火炉中通99.999%硫化氢气体至2×103Pa,再通99.999%高纯氮气至4×104Pa。开启加热电源开关,以每分钟7.6℃的升温速率从室温升至530~600℃,在530~600℃下保持15~20分钟,然后自然冷却至室温。加热过程中通过铠装K型热偶监测衬底温度。Close the angle valve of the mechanical pump, first pass 99.999% hydrogen sulfide gas to 2×10 3 Pa into the annealing furnace, and then pass 99.999% high-purity nitrogen gas to 4×10 4 Pa. Turn on the heating power switch, raise the temperature from room temperature to 530-600 °C at a rate of 7.6 °C per minute, keep at 530-600 °C for 15-20 minutes, and then cool naturally to room temperature. The substrate temperature was monitored by armored K-type thermocouples during the heating process.
优选地,高温的退火的温度为550℃,退火时间为15分钟。550℃达到铜锌锡硫(CZTS)前驱体薄膜的结晶温度,在550℃下退火15分钟,能够形成致密的CZTS光吸层,得到高质量的太阳能电池的光吸收层。Preferably, the high-temperature annealing temperature is 550° C., and the annealing time is 15 minutes. 550°C reaches the crystallization temperature of the copper-zinc-tin-sulfur (CZTS) precursor film, and annealing at 550°C for 15 minutes can form a dense CZTS light-absorbing layer and obtain a high-quality solar cell light-absorbing layer.
在高温退火过程中,锡覆盖层中的Sn不断的与H2S气体发生反应生成SnS2,SnS2不断地挥发,锡覆盖层最终被除去,不影响最终得到太阳能电池的光吸收层。During the high-temperature annealing process, the Sn in the tin cap layer continuously reacts with H 2 S gas to generate SnS 2 , and the SnS 2 is continuously volatilized, and the tin cap layer is finally removed without affecting the final light absorption layer of the solar cell.
待衬底温度冷却至室温后,开机械泵角阀,将退火炉抽至0Pa,关闭机械泵角阀,通99.999%高纯氮气至5×104Pa,再开机械泵角阀抽真空至0Pa,清洗退火炉内气体,防止硫化氢气体残留在退火炉中。关闭机械泵角阀,通99.999%高纯氮气至1×105Pa,打开退火炉腔室,取出成品。After the substrate temperature is cooled to room temperature, turn on the angle valve of the mechanical pump, pump the annealing furnace to 0 Pa, close the angle valve of the mechanical pump, pass 99.999% high-purity nitrogen to 5×10 4 Pa, and then turn on the angle valve of the mechanical pump to evacuate to 0Pa, clean the gas in the annealing furnace to prevent hydrogen sulfide gas from remaining in the annealing furnace. Close the mechanical pump angle valve, pass 99.999% high-purity nitrogen gas to 1×10 5 Pa, open the annealing furnace chamber, and take out the finished product.
针对铜锌锡硒薄膜前驱体:For copper zinc tin selenium thin film precursor:
退火炉中放入蒸发舟,蒸发舟中放置硒颗粒,加热蒸发舟至200℃,通入99.999%高纯氮气至4×104Pa。开启加热电源开关,以每分钟7.6℃的升温速率从室温升至530~600℃,在530~600℃下保持15~20分钟,然后自然冷却至室温。加热过程中通过铠装K型热偶监测衬底温度。Put an evaporating boat into the annealing furnace, place selenium particles in the evaporating boat, heat the evaporating boat to 200°C, and feed 99.999% high-purity nitrogen gas to 4×10 4 Pa. Turn on the heating power switch, raise the temperature from room temperature to 530-600 °C at a rate of 7.6 °C per minute, keep at 530-600 °C for 15-20 minutes, and then cool naturally to room temperature. The substrate temperature was monitored by armored K-type thermocouples during the heating process.
优选地,高温退火的温度为550℃,退火时间为15分钟。550℃达到铜锌锡硒(CZTSe)前驱体薄膜的结晶温度,在550℃下退火15分钟,能够形成致密的CZTSe光吸层,得到高质量的太阳能电池的光吸收层。Preferably, the high temperature annealing temperature is 550° C., and the annealing time is 15 minutes. 550°C reaches the crystallization temperature of the copper-zinc-tin-selenium (CZTSe) precursor thin film, and annealing at 550°C for 15 minutes can form a dense CZTSe light-absorbing layer and obtain a high-quality light-absorbing layer for solar cells.
在高温退火过程中,锡覆盖层中的Sn不断的与硒蒸汽发生反应生成SnSe2,SnSe2不断地挥发,锡覆盖层最终被除去,不影响最终得到太阳能电池的光吸收层。During the high-temperature annealing process, the Sn in the tin cap layer continuously reacts with the selenium vapor to form SnSe 2 , and the SnSe 2 is continuously volatilized, and the tin cap layer is finally removed without affecting the final light absorbing layer of the solar cell.
当氮气分压为4×104Pa,蒸发舟的温度为200℃时,硒蒸汽的分压为2×103Pa。当需要调整硒蒸汽分压时,可以通过调整蒸发舟的温度改变硒蒸汽的分压。When the nitrogen partial pressure is 4×10 4 Pa and the temperature of the evaporation boat is 200° C., the partial pressure of the selenium vapor is 2×10 3 Pa. When the partial pressure of the selenium vapor needs to be adjusted, the partial pressure of the selenium vapor can be changed by adjusting the temperature of the evaporation boat.
退火后的光吸收层,观察成品表面呈灰色,均匀不反光,水冲后不脱落。用万用表测量其对角电阻在500-700千欧左右,锡覆盖层的Sn已经完全硫化挥发。The light-absorbing layer after annealing is observed to be gray on the surface of the finished product, uniform and non-reflective, and does not fall off after being washed with water. The diagonal resistance measured by a multimeter is about 500-700 kilohms, and the Sn of the tin covering layer has been completely volatilized and volatilized.
在高温退火过程中还通入高纯氮气,以避免层叠有锡覆盖层的金属薄膜前驱体被氧化。可以理解,在MBE腔体内退火时,由于MBE腔体内部始终保持高真空(<10-5Pa),环境中不会有氧气等氧化性气体存在,金属薄膜前躯体不会被氧化,因此,可以直接在高真空MBE中退火,不用通入保护性的惰性气体。During the high-temperature annealing process, high-purity nitrogen gas is also introduced to prevent the metal film precursor laminated with the tin capping layer from being oxidized. It can be understood that during annealing in the MBE cavity, since the interior of the MBE cavity is always kept at a high vacuum (<10 -5 Pa), there will be no oxidizing gases such as oxygen in the environment, and the precursor of the metal film will not be oxidized. Therefore, It can be annealed directly in high vacuum MBE without introducing protective inert gas.
采用共蒸发制备金属薄膜前驱体时,高温退火的步骤也在MBE腔体内直接进行,而无需将样品取出再放入退火炉中,操作方便。When the metal film precursor is prepared by co-evaporation, the high-temperature annealing step is also directly carried out in the MBE cavity, without taking out the sample and putting it into the annealing furnace, which is convenient to operate.
退火过程直接在MBE腔体内继续进行。Se源炉的温度保持210℃,打开Se源炉挡板,样品台温度以每分钟15℃的升温速率从200℃匀速升温至550℃,用时23.3分钟,到达550℃后保持10分钟,关闭样品台加热电源,使样品自然冷却,当样品温度低于250℃时关闭Se源炉挡板,退火结束,取出样品,即得到太阳能电池的CZTSe光吸收层。The annealing process continues directly inside the MBE chamber. The temperature of the Se source furnace was maintained at 210°C, the baffle of the Se source furnace was opened, and the temperature of the sample stage was raised from 200°C to 550°C at a constant rate of 15°C per minute, which took 23.3 minutes, and kept for 10 minutes after reaching 550°C, and the sample was closed Stand heating power supply to cool the sample naturally. When the temperature of the sample is lower than 250°C, close the Se source furnace baffle. After the annealing is completed, take out the sample to obtain the CZTSe light absorption layer of the solar cell.
当成品表面的锡覆盖层未彻底硫化挥发时,样品泛白,对角电阻只有几百欧,当成品表面的锡覆盖层已经硫化但是未彻底挥发时,样品颜色较深,对角电阻为几千欧。遇到以上两种情况,对于CZTS光吸收层的制备,需调整锡覆盖层的厚度、或调整H2S浓度、或调整H2S氛围下前躯体的退火时间,以保证锡覆盖层中Sn的完全挥发。对于CZTSe光吸收层的制备,需要调整退火炉中Se蒸发舟或源炉的温度,同时调整Se蒸发舟中Se颗粒的量。When the tin covering layer on the surface of the finished product is not volatilized completely, the sample is whitish, and the diagonal resistance is only a few hundred ohms. thousand ohms. In the above two situations, for the preparation of the CZTS light-absorbing layer, it is necessary to adjust the thickness of the tin covering layer, or adjust the H 2 S concentration, or adjust the annealing time of the precursor under the H 2 S atmosphere, so as to ensure that the Sn in the tin covering layer completely volatile. For the preparation of the CZTSe light absorbing layer, it is necessary to adjust the temperature of the Se evaporation boat or the source furnace in the annealing furnace, and at the same time adjust the amount of Se particles in the Se evaporation boat.
上述太阳能电池的光吸收层的制备方法,在金属薄膜前驱体的表面形成锡覆盖层,利用锡覆盖层阻止在高温退火过程中,铜锌锡硫薄膜前驱体内SnS2的挥发或铜锌锡硒薄膜前驱体内SnSe2的挥发,从而达到抑制金属薄膜前驱体内Sn元素流失的目的,铜锌锡硫薄膜前驱体或铜锌锡硒薄膜前驱体经过退火形成致密的CZTS晶体或CZTSe晶体后,锡覆盖层中的Sn在硫化氢气氛下逐渐形成SnS2并脱离CZTS晶体表面,或在硒气氛下形成SnSe2并脱离CZTSe晶体表面,这个过程不会影响到CZTS晶体或CZTSe晶体的组分,避免了SnS2或SnSe2的挥发而导致Sn的流失,从而制备得到质量较高的CZTS光吸收层或CZTSe光吸收层。The preparation method of the light-absorbing layer of the above-mentioned solar cell forms a tin covering layer on the surface of the metal thin film precursor, and utilizes the tin covering layer to stop in the high-temperature annealing process, the volatilization of SnS in the copper-zinc-tin- sulfur film precursor or the copper-zinc-tin-selenide The volatilization of SnSe 2 in the thin film precursor can achieve the purpose of suppressing the loss of Sn element in the metal thin film precursor. The Sn in the layer gradually forms SnS2 and detaches from the CZTS crystal surface under the hydrogen sulfide atmosphere, or forms SnSe2 and detaches from the CZTSe crystal surface under the selenium atmosphere. This process will not affect the composition of the CZTS crystal or CZTSe crystal, avoiding the The volatilization of SnS 2 or SnSe 2 leads to the loss of Sn, thereby preparing a higher-quality CZTS light-absorbing layer or CZTSe light-absorbing layer.
上述太阳能电池的光吸收层的制备方法绿色无污染,对设备要求低,操作简单易行,适合在实验室研究和工业化生产中广泛使用。The preparation method of the light-absorbing layer of the solar cell is green and pollution-free, has low equipment requirements, is simple and easy to operate, and is suitable for wide use in laboratory research and industrial production.
以下通过具体实施例对上述太阳能电池的光吸收层的制备方法作进一步说明。The method for preparing the light absorbing layer of the above solar cell will be further described below through specific examples.
实施例1Example 1
制备太阳能电池的光吸收层Fabrication of light absorbing layers for solar cells
1、共蒸发法制备铜锌锡硒薄膜前驱体1. Preparation of copper zinc tin selenium thin film precursor by co-evaporation method
将镀有150nm厚度的钼背电极层的玻璃衬底放在MBE样品台上,打开样品台旋转开关,将Cu源炉、ZnSe源炉、Sn源炉、Se源炉和样品台的温度分别设为1210℃、765℃、1140℃、210℃和200℃,同时打开Cu源炉挡板、ZnSe源炉挡板、Sn源炉挡板、Se源炉挡板和样品台挡板,蒸镀720秒,得到铜锌锡硒薄膜前驱体,该铜锌锡硒薄膜前躯体的元素的摩尔比为Cu:Zn:Sn:Se=1.8:1.1:1.3:3.9;Place the glass substrate coated with a molybdenum back electrode layer with a thickness of 150nm on the MBE sample stage, turn on the rotary switch of the sample stage, and set the temperature of the Cu source furnace, the ZnSe source furnace, the Sn source furnace, the Se source furnace and the sample stage respectively. At 1210°C, 765°C, 1140°C, 210°C and 200°C, open the Cu source furnace baffle, ZnSe source furnace baffle, Sn source furnace baffle, Se source furnace baffle and sample stage baffle at the same time, vapor deposition 720 Second, obtain copper zinc tin selenium thin film precursor, the mol ratio of the element of this copper zinc tin selenium thin film precursor is Cu:Zn:Sn:Se=1.8:1.1:1.3:3.9;
2、蒸发法制备锡覆盖层2. Preparation of tin coating by evaporation method
将MBE的Sn源炉的温度在1140℃保持10分钟,待Sn束流稳定后,按顺序依次打开样品旋转电源、样品台挡板和Sn源炉挡板。蒸镀3分钟后依次关闭Sn源炉挡板、样品台挡板和样品旋转电源。蒸镀结束,冷却30分钟后形成层叠于金属薄膜前驱体上的锡覆盖层,得到层叠有锡覆盖层的铜锌锡硒薄膜前驱体,其中,锡覆盖层的厚度为150纳米;Keep the temperature of the Sn source furnace of MBE at 1140°C for 10 minutes. After the Sn beam current is stable, turn on the sample rotation power supply, the sample stage baffle and the Sn source furnace baffle in sequence. After 3 minutes of evaporation, turn off the Sn source furnace baffle, the sample stage baffle and the sample rotation power supply in sequence. Evaporation is finished, after cooling for 30 minutes, a tin coating layer laminated on the metal film precursor is formed to obtain a copper-zinc-tin-selenium film precursor laminated with a tin coating layer, wherein the thickness of the tin coating layer is 150 nanometers;
3、高温退火3. High temperature annealing
退火过程直接在MBE腔体内继续进行。Se源炉的温度保持210℃,打开Se源炉挡板,样品台温度从200℃匀速升温至550℃,用时15分钟,到达550℃后保持10分钟,关闭样品台加热电源,使样品自然冷却,当样品温度低于250℃时关闭Se源炉挡板,退火结束,取出样品,即得到太阳能电池的CZTSe光吸收层。The annealing process continues directly inside the MBE chamber. The temperature of the Se source furnace is maintained at 210°C. Open the baffle of the Se source furnace. The temperature of the sample stage is raised from 200°C to 550°C at a constant speed. It takes 15 minutes. After reaching 550°C, keep it for 10 minutes. Turn off the heating power of the sample stage and let the sample cool naturally. , when the temperature of the sample is lower than 250°C, close the Se source furnace baffle, the annealing is finished, and the sample is taken out to obtain the CZTSe light absorbing layer of the solar cell.
实施例2Example 2
制备太阳能电池的光吸收层Fabrication of light absorbing layers for solar cells
1、共溅射法制备铜锌锡硫薄膜前驱体1. Co-sputtering method to prepare copper-zinc-tin-sulfur thin film precursor
将镀有150nm厚度的钼背电极层的玻璃衬底放在磁控溅射样品台上,打开样品台旋转开关,将Cu靶、ZnS靶和SnS2靶的功率分别设为60w、75w和70w,预溅射10分钟后,同时打开Cu靶挡板、ZnS靶挡板、SnS2靶挡板和衬底挡板,共溅射1小时,得到铜锌锡硫薄膜前驱体,铜锌锡硫薄膜前驱体的组分的摩尔比为Cu:Zn:Sn:Se=1.8:1.1:1.3:3.9;Place the glass substrate coated with a molybdenum back electrode layer with a thickness of 150nm on the magnetron sputtering sample stage, turn on the rotary switch of the sample stage, and set the power of Cu target, ZnS target and SnS2 target to 60w, 75w and 70w respectively , after pre-sputtering for 10 minutes, open the Cu target shutter, ZnS target shutter, SnS2 target shutter and substrate shutter at the same time, and sputter for 1 hour to obtain the copper-zinc-tin-sulfur thin film precursor, copper-zinc-tin-sulfur The molar ratio of the components of the film precursor is Cu:Zn:Sn:Se=1.8:1.1:1.3:3.9;
2、溅射法制备锡覆盖层2. Preparation of tin coating by sputtering
Sn靶的功率设为50w,预溅射10分钟后,打开Sn靶挡板,溅射10分钟后关闭Sn靶挡板,溅射结束,冷却30分钟后形成层叠于金属薄膜前驱体上的锡覆盖层,得到层叠有锡覆盖层的铜锌锡硫薄膜前驱体,其中,锡覆盖层的厚度为150纳米;The power of the Sn target is set to 50w. After 10 minutes of pre-sputtering, the Sn target baffle is opened, and the Sn target baffle is closed after 10 minutes of sputtering. After the sputtering is over, the tin laminated on the metal film precursor is formed after cooling for 30 minutes. Covering layer, obtain the copper zinc tin sulfur thin film precursor that is laminated with tin covering layer, wherein, the thickness of tin covering layer is 150 nanometers;
3、取出层叠有锡覆盖层的铜锌锡硫前驱体薄膜,放入退火炉中,用机械泵抽真空至薄膜真空规读数为0Pa。用计时器计时继续抽5分钟,以保证退火炉清洁。然后,先向退火炉中通H2S(纯度为99.999%)气体至2×103Pa,再通99.999%高纯氮气至4×104Pa。以每分钟7.6℃的升温速率从室温升至550℃,在550℃保持15分钟,然后自然冷却至室温。加热过程中通过铠装K型热偶监测衬底温度。待衬底温度冷却至室温后,清洗退火炉中残余的H2S气氛,取出样品,即得到太阳能电池的CZTS光吸收层。3. Take out the copper-zinc-tin-sulfur precursor film laminated with the tin coating layer, put it into the annealing furnace, and use a mechanical pump to evacuate until the reading of the film vacuum gauge is 0Pa. Continue pumping for 5 minutes with a timer to ensure that the annealing furnace is clean. Then, H 2 S (purity 99.999%) gas is passed to the annealing furnace to 2×10 3 Pa, and then 99.999% high-purity nitrogen gas is passed to 4×10 4 Pa. Raise from room temperature to 550°C at a rate of 7.6°C per minute, keep at 550°C for 15 minutes, and then cool naturally to room temperature. The substrate temperature was monitored by armored K-type thermocouples during the heating process. After the substrate temperature is cooled to room temperature, the remaining H 2 S atmosphere in the annealing furnace is cleaned, and the sample is taken out to obtain the CZTS light absorption layer of the solar cell.
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and the description thereof is relatively specific and detailed, but should not be construed as limiting the patent scope of the present invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.
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