CN105803392A - Preparation method for Na-doped Cu<2>ZnSn(S<1-x>Se<x>)<4> film - Google Patents
Preparation method for Na-doped Cu<2>ZnSn(S<1-x>Se<x>)<4> film Download PDFInfo
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Abstract
The invention discloses a preparation method for a Na-doped Cu<2>ZnSn(S<1-x>Se<x>)<4> film, belonging to the technical field of preparation of optical films. The method comprises the following steps: 1) cleaning a substrate; 2) carrying out magnetron sputtering of Cu<2>ZnSn(S<1-x>Se<x>)<4> (0 <= x <= 1) and co-sputtering of NaF at the same time or carrying out alternative layered preparation of a Cu<2>ZnSn(S<1-x>Se<x>)<4> film and a NaF film; and 3) subjecting the film to heat treatment. With the above-mentioned two Na doping manners, Na doping uniformity of the Cu<2>ZnSn(S<1-x>Se<x>)<4> film can be effectively improved, so the photoelectric conversion efficiency of a Cu<2>ZnSn(S<1-x>Se<x>)<4> film solar battery is improved.
Description
Technical field
The present invention relates to a kind of Na doping Cu2ZnSn(S1-xSex)4The preparation method of thin film, belongs to Deposition Techniques for Optical Thin Films field.
Background technology
In recent years, Cu2ZnSn(S1-xSex)4Thin-film solar cells becomes the focus of various countries' research, Cu2ZnSn(S1-xSex)4Cu (In, Ga) (S, Se) is replaced with Zn and the Sn of rich content in the earth's crust2In rare precious metals In and Ga, greatly reduce the preparation cost of solaode, therefore, Cu2ZnSn(S1-xSex)4It it is the absorbing layer of thin film solar cell material of a kind of sustainable development.At present, Cu2ZnSn(S1-xSex)4The efficiency of thin-film solar cells is significantly improved, at the beginning of 2014, and Cu2ZnSn(S1-xSex)4The Laboratory efficiencies record of hull cell has reached 12.6% [WangW.etal., Adv.EnergyMater., 4 (2014), 1301465], efficiency quick, significantly improve so that Cu2ZnSn(S1-xSex)4The practical application of thin-film solar cells is possibly realized.
In current research, Cu2ZnSn(S1-xSex)4The thin film overwhelming majority is all deposited in soda-lime glass substrate (SLG), it has been found that, the Na atom in substrate can diffuse into thin film, and then improves the physical property of thin film.Na diffusion couple Cu2ZnSn(S1-xSex)4Beneficial effect be mainly reflected in some [TejasP.etal. following, Sol.EnergyMater.Sol.Cells, 95 (2011), 1001]: 1) Na doping energy enhanced film lattice structure, increase thin film crystallite dimension, reduce number of grain boundaries, thus efficiently reducing the compound of carrier；2) Na ion pair thin film crystal grain also has passivation, makes crystal grain pile up more tight, improves thin film compactness；3) in electric property, the introducing of Na ion so that Na occupies Cu point position and forms defect, adds number of cavities, significantly improve carrier concentration in thin film, and then increase film conductivity.At present, to Cu2ZnSn(S1-xSex)4Thin film introduces Na mainly through three kinds of modes: 1) adopt soda-lime glass as the backing material [GuoQ.J.etal., J.Am.Chem.Soc., 132 (2010), 17384] of thin-film solar cells；2) adopt thermal evaporation techniques, bottom thin film or top evaporation one layer of NaF [LiJ.V.etal., Appl.Phys.Lett., 102 (2013), 163905]；3) thin film is immersed in the solution containing Na ion [GuoQ.etal., Prog.Photovoltaics, 21 (2013), 64].Above-mentioned Na doping way easily causes the inhomogeneities of Na doping in thin film, makes there is Na Concentraton gradient in thin film, impact doping effect.
Cu2ZnSn(S1-xSex)4The preparation method of thin film mainly includes liquid phase method [Teodork.etal., Adv.EnergyMater., 3 (2013), 34-38], vacuum vapor deposition method [WangK.etal, Appl.Phys.Lett., 97 (2010), 143508] and magnetron sputtering method [HironoriK.etal., ThinSolidFilms, 517 (2009), 2455-2460].Liquid phase method generally uses the organic solvent that a large amount of contaminative is stronger, such as toluene, hydrazine etc., is unfavorable for sustainable development；It is good that vacuum vapor deposition method prepares little area thin film quality, but is difficult to ensure that when preparing large area film uniformity of film and the controllability of element proportioning, raw material availability and production efficiency are relatively low, causes that film production is relatively costly, is unfavorable for large-scale industrial production；The raw-material utilization rate of sputtering method is high, it is possible to regulate the stoicheiometry of each element better, improves preparation repeatability, is suitable for manufacturing area battery.
To sum up, it is necessary to propose a kind of based on magnetron sputtering technique, preparation Na doping Cu2ZnSn(S1-xSex)4The method of thin film, improves the Na uniform doping in thin film, weakens and even eliminates Na Concentraton gradient that may be present in thin film, improves Cu further2ZnSn(S1-xSex)4Thin-film solar cell photoelectric conversion efficiency.
Summary of the invention
It is an object of the invention to provide a kind of Na doping Cu2ZnSn(S1-xSex)4The preparation method of thin film.The method can improve Na uniform doping in thin film, weakens and even avoids existing doping way to be likely to the Na doping content gradient caused, thus improving the performance of thin-film solar cells further.
For achieving the above object, the present invention is by the following technical solutions:
A kind of Na doping Cu2ZnSn(S1-xSex)4The preparation method of thin film, adopts conventional magnetically controlled sputter method to prepare Na doping Cu on substrate2ZnSn(S1-xSex)4(0≤x≤1) thin film, it is characterised in that comprise the following steps:
1) substrate is carried out；
2) Cu is prepared at magnetron sputtering2ZnSn(S1-xSex)4Cosputtering NaF in thin-film process, or alternatively layered prepares Cu2ZnSn(S1-xSex)4Thin film and NaF thin film；
3) thin film is carried out heat treatment.
Cu is prepared at magnetron sputtering2ZnSn(S1-xSex)4In thin-film process cosputtering NaF adopt two ways, namely continue or etc. time slot cosputtering NaF.
Wherein, NaF target can individually occupy a target position, with preparation Cu2ZnSn(S1-xSex)4Target cosputtering together needed for thin film, cosputtering NaF adopt continue cosputtering mode or etc. time slot cosputtering mode.Continue cosputtering NaF to refer to, from preparation Cu2ZnSn(S1-xSex)4The each target as sputter of thin film starts to sputtering to terminate, and NaF target is in sputtering state all the time, i.e. the sputtering time of NaF and Cu2ZnSn(S1-xSex)4The film preparation time is equal；Refer to Deng time slot cosputtering NaF, from preparation Cu2ZnSn(S1-xSex)4The each target as sputter of thin film starts to sputtering to terminate, NaF target as sputter a period of time, stop sputtering a period of time, then sputter a period of time again, then stop sputtering a period of time, move in circles, the time sputtered each time and power are all equal, and sputtering time is less than or equal to 30min each time, and the time stopping sputtering each time is all equal, stop the time of sputtering each time less than or equal to 15min, and NaF target as sputter number of times is be more than or equal to 2 times.Above two mode is all conducive to improving the Na uniform doping of thin film.
NaF can also with preparation Cu2ZnSn(S1-xSex)4Needed for thin film, the one in target makes composite target material, continues cosputtering NaF, i.e. NaF sputtering time and preparation Cu2ZnSn(S1-xSex)4The time of thin film is equal, it is achieved to Cu2ZnSn(S1-xSex)4The Na doping of thin film.Wherein, the preparation of composite target material includes two ways: one is in preparation of target materials process, directly mixes NaF in target；Another kind is that the NaF small pieces of several consistent size are pasted onto a certain target material surface, makes composition target.
Alternatively layered prepares Cu2ZnSn(S1-xSex)4Thin film and NaF thin film refer to, at preparation Cu2ZnSn(S1-xSex)4In thin-film process, do not sputter NaF, in preparation NaF thin-film process, do not prepare Cu2ZnSn(S1-xSex)4Thin film, Cu2ZnSn(S1-xSex)4The alternately preparation of thin film and NaF thin film.In the process, the sputtering number of times of NaF is be more than or equal to 2 times, and the monolayer NaF thin film sputtering time, between every two-layer NaF membrane-film preparation process, NaF target stopped sputtering time less than or equal to 15min less than or equal to 30min.
Film thermal processes can improve Na uniform doping in thin film further, allows Na spread further in the film, weakens and even eliminates Na Concentraton gradient that may be present in thin film.Film thermal processing links includes following three kinds of situations: is arranged in thin film sputtering deposition process, namely substrate is heated；Or, after being positioned at thin film sputtering deposition process, i.e. thin film subsequent heat treatment；Or, in thin film sputtering deposition process and after process, all have heat treatment.Meanwhile, from Cu2ZnSn(S1-xSex)4Film preparation angle considers, for preventing element evaporation in thin film, film thermal treatment temperature controls below 600 DEG C.Wherein, the heat treatment time in film deposition process is equal with the thin film deposition time, and the heat treatment time after film deposition process is less than or equal to 2h.
Adopt the Na doping Cu that method described in present patent application is finally prepared2ZnSn(S1-xSex)4Thin film, Na doping molar concentration Na/ (Cu+Zn+Sn) is 0 < Na doping molar concentration Na/ (Cu+Zn+Sn)≤3%.
It is an advantage of the current invention that:
In current research, to Cu2ZnSn(S1-xSex)4Film doping Na mainly adopts three kinds of modes: 1) adopt soda-lime glass as the backing material of thin film；2) at Cu2ZnSn(S1-xSex)4Bottom thin film or top one layer of NaF of evaporation；3) thin film is immersed in the solution containing Na ion.Above-mentioned doping way easily causes exists Na Concentraton gradient in thin film, impact doping effect.The invention provides a kind of Na doping Cu2ZnSn(S1-xSex)4The preparation method of thin film, prepares Cu at magnetron sputtering2ZnSn(S1-xSex)4Cosputtering NaF in thin-film process, or alternatively layered prepares Cu2ZnSn(S1-xSex)4Thin film and NaF thin film, then carry out heat treatment to thin film, improves Na uniform doping in thin film, weakens and even avoids the Na doping content gradient that existing doping way is likely to cause, thus improving the performance of thin-film solar cells further.
Accompanying drawing explanation
Fig. 1 is one Na of the present invention doping Cu2ZnSn(S1-xSex)4The preparation method flow chart of thin film.
Detailed description of the invention
As it is shown in figure 1, the present invention " a kind of Na doping Cu2ZnSn(S1-xSex)4The preparation method of thin film ", mainly include three steps: 1) substrate is carried out；2) Cu is prepared at magnetron sputtering2ZnSn(S1-xSex)4Cosputtering NaF in (0≤x≤1) thin-film process, or alternatively layered prepares Cu2ZnSn(S1-xSex)4Thin film and NaF thin film；3) thin film is carried out heat treatment, including three kinds of situations: in thin film sputtering deposition process, substrate is heated；Or, after thin film sputtering deposition process completes, thin film is carried out subsequent heat treatment；Or, in thin film sputtering deposition process and after deposition process, all thin film is carried out heat treatment.
The enforcement of the present invention can be effectively improved Cu2ZnSn(S1-xSex)4Middle Na uniform doping.
Embodiment 1
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of thin film, NaF target individually occupies a target position, at Cu2ZnSnS4(x=0) membrane-film preparation process continues cosputtering NaF, it is achieved to Cu2ZnSnS4The Na doping of thin film, film doping concentration is 0.1%, particularly as follows:
Step 1: substrate cleans:
Sequentially using deionized water, acetone and dehydrated alcohol respectively soda lime glass substrates to be carried out ultrasonic cleaning, scavenging period is 10min, blows the ethanol of substrate surface remaining off by nitrogen gun.
Step 2: film preparation:
Preparation Na doping Cu2ZnSnS4Thin film.Target is Cu, ZnS, SnS2And NaF, sputter gas is Ar gas, and sputtering pressure 0.25Pa, NaF target individually occupies a target position, adopts the mode continuing cosputtering NaF that thin film is carried out Na doping, and wherein, Cu target adopts d.c. sputtering mode, ZnS, SnS2Radio-frequency sputtering mode, Cu, ZnS, SnS is adopted with NaF target2With the Sputtering power density of NaF target respectively 0.7W/cm2、4.3W/cm2、1.3W/cm2And 0.3W/cm2, sputtering time 30min.
Step 3: film thermal processes:
After film preparation completes, thin film is carried out subsequent heat treatment.Being placed in tube furnace by thin film, meanwhile, put into the quartz boat equipped with S powder in tube furnace quartz ampoule, thin film and quartz boat heat respectively, with N2As sulfuration carrier gas.First quartz boat is heated to 200 DEG C, stablizes 30min, then to Cu2ZnSnS4Thin film carries out heat treatment, and heat treatment temperature is 580 DEG C, heat time heating time 2h.Heating naturally cools to room temperature after terminating, in cooling procedure, and N2Flow is constant, steady air current.
Embodiment 2
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of thin film, NaF target individually occupies a target position, at Cu2ZnSnSe4(x=1) membrane-film preparation process medium while gap cosputtering NaF, it is achieved to Cu2ZnSnSe4The Na doping of thin film, film doping concentration is 1.2%, particularly as follows:
Step 1: substrate cleans:
Sequentially using deionized water, acetone and dehydrated alcohol respectively soda lime glass substrates to be carried out ultrasonic cleaning, scavenging period is 10min, blows the ethanol of substrate surface remaining off by nitrogen gun.
Step 2: film preparation:
Preparation Na doping Cu2ZnSnSe4Thin film.Target is Cu, ZnSe, SnSe2And NaF, sputter gas is Ar gas, and sputtering pressure 0.5Pa, NaF target individually occupies a target position, and thin film is carried out Na doping by the mode of the time slot cosputtering NaF such as employing, and wherein, Cu target adopts d.c. sputtering mode, ZnSe, SnSe2Radio-frequency sputtering mode, Cu, ZnSe, SnSe is adopted with NaF target2With the Sputtering power density of NaF target respectively 0.9W/cm2、4.3W/cm2、1.3W/cm2And 1.4W/cm2NaF target starts cosputtering after all the other target as sputter 15min, sputtering time is 30min, then stop sputtering NaF15min then cosputtering NaF30min, stop in the time of sputtering at NaF target, all the other targets still prepare thin film at cosputtering, in whole process, NaF cosputtering 2 times, the total sputtering time 90min of thin film.
Step 3: film thermal processes:
In membrane-film preparation process, substrate being heated, heating-up temperature is 525 DEG C, and heat time heating time is equal with the thin film sputtering time, for 30min.
Embodiment 3
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of thin film, NaF target individually occupies a target position, at Cu2ZnSn(S0.6Se0.4)4(x=0.4) membrane-film preparation process medium while gap cosputtering NaF, it is achieved to Cu2ZnSn(S0.6Se0.4)4The Na doping of thin film, film doping concentration is 3%, particularly as follows:
Step 1: substrate cleans:
Sequentially using deionized water, acetone and dehydrated alcohol respectively soda lime glass substrates to be carried out ultrasonic cleaning, scavenging period is 10min, blows the ethanol of substrate surface remaining off by nitrogen gun.
Step 2: film preparation:
Preparation Na doping Cu2ZnSn(S0.6Se0.4)4Thin film.Target is Cu, ZnS and SnSe2, sputter gas is Ar gas, and sputtering pressure 0.5Pa, NaF target individually occupies a target position, and thin film is carried out Na doping by the mode of the time slot cosputtering NaF such as employing, and wherein, Cu target adopts d.c. sputtering mode, ZnS, SnSe2Radio-frequency sputtering mode, Cu, ZnS, SnSe is adopted with NaF target2With the Sputtering power density of NaF target respectively 0.8W/cm2、3.5W/cm2、1.1W/cm2And 3W/cm2, NaF target starts cosputtering, sputtering time 10min after all the other target as sputter 5min, then stop sputtering NaF5min then cosputtering NaF10min, circulate 2 times, stopping in the time of sputtering at NaF target, all the other targets still prepare thin film, whole process sputtering time 30min at cosputtering.
Step 3: film thermal processes:
After film preparation completes, thin film is carried out heat treatment.Being placed in tube furnace by thin film, meanwhile, put into the quartz boat equipped with S powder in tube furnace quartz ampoule, thin film and quartz boat heat respectively, with N2As sulfuration carrier gas.First quartz boat being heated to 200 DEG C, stablize 30min, then thin film is carried out heat treatment, heat treatment temperature is 550 DEG C, heat time heating time 1h.Heating naturally cools to room temperature after terminating, in cooling procedure, and N2Flow is constant, steady air current.
Embodiment 4
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The NaF small pieces of formed objects are pasted onto on ZnS target and make ZnS/NaF composition target, at Cu by the preparation method of thin film2ZnSnS4(x=0) membrane-film preparation process continues cosputtering NaF, it is achieved to Cu2ZnSnS4The Na doping of thin film, film doping concentration is 1%, particularly as follows:
Step 1: substrate cleans:
Sequentially using deionized water, acetone and dehydrated alcohol soda lime glass substrates respectively to carry out ultrasonic cleaning, scavenging period is 10min, blows the ethanol of substrate surface remaining off by nitrogen gun.
Step 2: film preparation:
Prepare the Cu of Na doping2ZnSnS4Thin film.Target is Cu target, ZnS/NaF composite target material and SnS2Target, sputter gas is Ar gas, sputtering pressure 0.25Pa, is pasted onto on ZnS target by NaF small pieces and makes composition target, continues cosputtering NaF, it is achieved the uniform Na of thin film is adulterated, and wherein, Cu target adopts d.c. sputtering mode, ZnS/NaF composition target and SnS2Target adopts radio-frequency sputtering mode, Cu target, ZnS/NaF composition target and SnS2The Sputtering power density of target respectively 0.4W/cm2、2.1W/cm2And 0.6W/cm2, sputtering time 30min.
Step 3: film thermal processes:
After film preparation completes, thin film is carried out heat treatment.Being placed in tube furnace by thin film, meanwhile, put into the quartz boat equipped with S powder in tube furnace quartz ampoule, thin film and quartz boat heat respectively, with N2As sulfuration carrier gas.First quartz boat being heated to 200 DEG C, stablize 30min, then thin film is carried out heat treatment, heat treatment temperature is 560 DEG C, heat time heating time 2h.Heating naturally cools to room temperature after terminating, in cooling procedure, and N2Flow is constant, steady air current.
Embodiment 5
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of thin film, mixes NaF in ZnS preparation of target materials process, makes ZnS/NaF composite target material, and then at Cu2ZnSn(S0.5Se0.5)4(x=0.5) membrane-film preparation process continues sputter NaF, it is achieved to Cu2ZnSnS4The Na doping of thin film, film doping concentration is 0.5%, particularly as follows:
Step 1: substrate cleans:
Sequentially using deionized water, acetone and dehydrated alcohol respectively soda lime glass substrates to be carried out ultrasonic cleaning, scavenging period is 10min, blows the ethanol of substrate surface remaining off by nitrogen gun.
Step 2: film preparation:
Preparation Na doping Cu2ZnSn(S0.5Se0.5)4Thin film.Target is Cu target, ZnS/NaF composite target material and SnSe2Target, sputter gas is Ar gas, sputtering pressure 0.5Pa, ZnS preparation of target materials process mixes NaF, makes ZnS/NaF composite target material, and then continue to sputter NaF in membrane-film preparation process, realize the uniform Na of thin film is adulterated, wherein, Cu target adopts d.c. sputtering mode, ZnS/NaF composition target and SnSe2Target adopts radio-frequency sputtering mode, Cu, ZnS/NaF and SnSe2The Sputtering power density of target respectively 0.7W/cm2、2.8W/cm2And 0.9W/cm2, sputtering time 30min.
Step 3: film thermal processes:
In membrane-film preparation process and film preparation terminate after carry out heat treatment respectively.To silicon 200 DEG C in membrane-film preparation process, heat time heating time is 30min；After film preparation completes, being placed in tube furnace by thin film, meanwhile, put into the quartz boat equipped with S powder in tube furnace quartz ampoule, thin film and quartz boat heat respectively, with N2As sulfuration carrier gas.First quartz boat being heated to 200 DEG C, stablize 30min, then thin film is carried out heat treatment, heat treatment temperature is 550 DEG C, heat time heating time 2h.Heating naturally cools to room temperature after terminating, in cooling procedure, and N2Flow is constant, steady air current.
Embodiment 6
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of thin film, adopts alternatively layered to prepare Cu2ZnSnS4(x=0) mode of thin film and NaF thin film, it is achieved to Cu2ZnSnS4The Na doping of thin film, film doping concentration is 2.5%, particularly as follows:
Step 1: substrate cleans:
Sequentially using deionized water, acetone and dehydrated alcohol respectively soda lime glass substrates to be carried out ultrasonic cleaning, scavenging period is 10min, blows the ethanol of substrate surface remaining off by nitrogen gun.
Step 2: film preparation:
Preparation Na doping Cu2ZnSnS4Thin film.Target is Cu, ZnS, SnS2With NaF target, employing alternatively layered prepares Cu2ZnSnS4(x=0) mode of thin film and NaF thin film, it is achieved the Na of thin film is adulterated, wherein, Cu, ZnS and SnS2Three target co-sputterings prepare Cu2ZnSnS4Thin film, the independent Slag coating NaF layer of NaF target, sputter gas is Ar gas, and sputtering pressure 0.5Pa, Cu target adopts d.c. sputtering mode, ZnS target, SnS2Target and NaF target adopt radio-frequency sputtering mode, Cu target, ZnS target, SnS2The Sputtering power density of target and NaF target respectively 0.9W/cm2、5W/cm2、1.6W/cm2And 1.6W/cm2, in the process, first, Cu, ZnS and SnS2Three target co-sputterings prepare Cu2ZnSnS4Layer 15min, then prepares NaF layer 30min, hockets with this, total sputtering time 90min, wherein, and Cu, ZnS and SnS2Three target co-sputterings 2 times, NaF target as sputter 2 times.
Step 3: film thermal processes:
After film preparation completes, thin film is carried out heat treatment.Being placed in tube furnace by thin film, meanwhile, put into the quartz boat equipped with S powder in tube furnace quartz ampoule, thin film and quartz boat heat respectively, with N2As sulfuration carrier gas.First quartz boat being heated to 200 DEG C, stablize 30min, then thin film is carried out heat treatment, heat treatment temperature is 540 DEG C, heat time heating time 2h.Heating naturally cools to room temperature after terminating, in cooling procedure, and N2Flow is constant, steady air current.
Embodiment 7
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of thin film, adopts alternatively layered to prepare Cu2ZnSnS4(x=0) mode of thin film and NaF thin film, it is achieved to Cu2ZnSnS4The Na doping of thin film, film doping concentration is 0.15%, particularly as follows:
Step 1: substrate cleans:
Sequentially using deionized water, acetone and dehydrated alcohol respectively soda lime glass substrates to be carried out ultrasonic cleaning, scavenging period is 10min, blows the ethanol of substrate surface remaining off by nitrogen gun.
Step 2: film preparation:
Preparation Na doping Cu2ZnSnS4Thin film.Target is Cu2ZnSnS4With NaF target, employing alternatively layered prepares Cu2ZnSnS4(x=0) mode of thin film and NaF thin film, it is achieved the Na of thin film is adulterated, wherein, Cu2ZnSnS4Preparation of target materials Cu2ZnSnS4Thin film, the independent Slag coating NaF layer of NaF target, sputter gas is Ar gas, sputtering pressure 0.25Pa, Cu2ZnSnS4Target and NaF target all adopt radio-frequency sputtering mode, and Sputtering power density is 3.5W/cm respectively2And 1.1W/cm2, in the process, first prepare Cu2ZnSnS4Layer 5min, then prepares NaF layer 1min, hockets with this, total sputtering time 30min, wherein, and Cu2ZnSnS4Target as sputter 5 times, NaF target as sputter 5 times.
Step 3: film thermal processes:
After film preparation completes, thin film is carried out heat treatment.Being placed in tube furnace by thin film, meanwhile, put into the quartz boat equipped with S powder in tube furnace quartz ampoule, thin film and quartz boat heat respectively, with N2As sulfuration carrier gas.First quartz boat being heated to 200 DEG C, stablize 30min, then thin film is carried out heat treatment, heat treatment temperature is 600 DEG C, heat time heating time 2h.Heating naturally cools to room temperature after terminating, in cooling procedure, and N2Flow is constant, steady air current.
Claims (9)
1. a Na doping Cu2ZnSn(S1-xSex)4The preparation method of thin film, wherein 0≤x≤1, it is characterised in that use conventional magnetically controlled sputter method, comprise the following steps:
1) substrate is carried out；
2) Cu is prepared at magnetron sputtering2ZnSn(S1-xSex)4Cosputtering NaF in thin-film process, or alternatively layered prepares Cu2ZnSn(S1-xSex)4Thin film and NaF thin film；
3) thin film is carried out heat treatment.
2. a kind of Na doping Cu according to claim 12ZnSn(S1-xSex)4The preparation method of thin film, it is characterised in that: prepare Cu at magnetron sputtering2ZnSn(S1-xSex)4In thin-film process cosputtering NaF adopt two ways, namely continue or etc. time slot cosputtering NaF.
3. a kind of Na doping Cu according to claim 1 and 22ZnSn(S1-xSex)4The preparation method of thin film, it is characterised in that: NaF target individually occupies a target position, with preparation Cu2ZnSn(S1-xSex)4Target cosputtering together needed for thin film, cosputtering NaF adopt continue cosputtering mode or etc. time slot cosputtering mode, according to lasting cosputtering NaF mode, the sputtering time of NaF and Cu2ZnSn(S1-xSex)4The film preparation time is equal；According to etc. time slot cosputtering NaF mode, NaF target as sputter number of times be more than or equal to 2 times, the NaF target single cosputtering time less than or equal to 30min, every twice cosputtering NaF interprocedual, NaF target stop sputtering time less than or equal to 15min.
4. a kind of Na doping Cu according to claim 1 and 22ZnSn(S1-xSex)4The preparation method of thin film, it is characterised in that: by NaF and preparation Cu2ZnSn(S1-xSex)4Needed for thin film, the one in target makes composite target material, continues cosputtering NaF, it is achieved to Cu2ZnSn(S1-xSex)4The Na doping of thin film, NaF target continues cosputtering time and Cu2ZnSn(S1-xSex)4The film preparation time is equal.
5. a kind of Na doping Cu according to claim 12ZnSn(S1-xSex)4The preparation method of thin film, it is characterised in that: prepare Cu at alternatively layered2ZnSn(S1-xSex)4In thin film and NaF thin-film process, NaF target individually occupies a target position, and the sputtering number of times of NaF is be more than or equal to 2 times, and the monolayer NaF thin film sputtering time is less than or equal to 30min, between every two-layer NaF membrane-film preparation process, NaF target stops sputtering time less than or equal to 15min.
6. a kind of Na doping Cu according to claim 12ZnSn(S1-xSex)4The preparation method of thin film, it is characterised in that: film thermal processing links includes following three kinds of situations: is arranged in thin film sputtering deposition process, namely substrate is heated；Or, after being positioned at thin film sputtering deposition process, i.e. thin film subsequent heat treatment；Or, in thin film sputtering deposition process and after process, all have heat treatment；Film thermal treatment temperature is less than or equal to 600 DEG C；Wherein, the heat treatment time in film deposition process is equal with the thin film deposition time, and the heat treatment time after film deposition process is less than or equal to 2h.
7. according to claim 1 or 2,5 or a kind of Na described in 6 adulterate Cu2ZnSn(S1-xSex)4The preparation method of thin film, it is characterised in that: the Na doping Cu finally prepared2ZnSn(S1-xSex)4In thin film, Na doping molar concentration Na/ (Cu+Zn+Sn) is 0 < Na doping molar concentration Na/ (Cu+Zn+Sn)≤3%.
8. a kind of Na doping Cu according to claim 32ZnSn(S1-xSex)4The preparation method of thin film, it is characterised in that: the Na doping Cu finally prepared2ZnSn(S1-xSex)4In thin film, Na doping molar concentration Na/ (Cu+Zn+Sn) is 0 < Na doping molar concentration Na/ (Cu+Zn+Sn)≤3%.
9. a kind of Na doping Cu according to claim 42ZnSn(S1-xSex)4The preparation method of thin film, it is characterised in that: the Na doping Cu finally prepared2ZnSn(S1-xSex)4In thin film, Na doping molar concentration Na/ (Cu+Zn+Sn) is 0 < Na doping molar concentration Na/ (Cu+Zn+Sn)≤3%.
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| CN114864752A (en) * | 2022-06-15 | 2022-08-05 | 金陵科技学院 | Method for improving residual stress of absorption layer of flexible CZTSSe thin-film solar cell and application |
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| CN102372302A (en) * | 2010-08-20 | 2012-03-14 | 华东师范大学 | Copper-zinc-tin-sulfur or copper-zinc-tin-selenium target for absorbed layer of thin-film solar battery, preparation method for target and application of target |
| WO2013062825A1 (en) * | 2011-10-27 | 2013-05-02 | Intermolecular, Inc. | Back-contact for thin film solar cells optimized for light trapping for ultrathin absorbers |
| CN104247036A (en) * | 2012-04-27 | 2014-12-24 | 法国圣戈班玻璃厂 | Method for producing the pentanary compound semiconductor cztsse doped with sodium |
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| CN102212780A (en) * | 2011-05-04 | 2011-10-12 | 四川大学 | Method for preparing p-type cadmium sulfide film |
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| CN114864752A (en) * | 2022-06-15 | 2022-08-05 | 金陵科技学院 | Method for improving residual stress of absorption layer of flexible CZTSSe thin-film solar cell and application |
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