CN105803392B - A kind of Na doping Cu2ZnSn(S1-xSex)4The preparation method of film - Google Patents
A kind of Na doping Cu2ZnSn(S1-xSex)4The preparation method of film Download PDFInfo
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Abstract
The invention discloses a kind of Na to adulterate Cu2ZnSn(S1‑xSex)4The preparation method of film belongs to Deposition Techniques for Optical Thin Films field.1) this method is the following steps are included: clean substrate；2) Cu is prepared in magnetron sputtering2ZnSn(S1‑xSex)4Cosputtering NaF or alternatively layered prepare Cu in (0≤x≤1) thin-film process2ZnSn(S1‑xSex)4Film and NaF film；3) film is heat-treated.The present invention can effectively improve Cu by using above two Na doping way2ZnSn(S1‑xSex)4The Na uniform doping of film, and then improve Cu2ZnSn(S1‑xSex)4The photoelectric conversion efficiency of thin-film solar cells.
Description
Technical field
The present invention relates to a kind of Na to adulterate Cu2ZnSn(S1-xSex)4The preparation method of film belongs to optical thin film preparation skill
Art field.
Background technique
In recent years, Cu2ZnSn(S1-xSex)4Thin-film solar cells becomes the hot spot of various countries' research, Cu2ZnSn(S1- xSex)4Replace Cu (In, Ga) (S, Se) with the Zn and Sn of rich content in the earth's crust2In rare precious metals In and Ga, greatly drop
The low preparation cost of solar battery, therefore, Cu2ZnSn(S1-xSex)4It is a kind of thin-film solar cells of sustainable development
Absorb layer material.Currently, Cu2ZnSn(S1-xSex)4The efficiency of thin-film solar cells is significantly improved, at the beginning of 2014,
Cu2ZnSn(S1-xSex)4The Laboratory efficiencies record of hull cell have reached 12.6% [Wang W.et al.,
Adv.Energy Mater., 4 (2014), 1301465], efficiency it is quick, significantly improve so that Cu2ZnSn(S1-xSex)4It is thin
The practical application of film solar cell is possibly realized.
In current research, Cu2ZnSn(S1-xSex)4The film overwhelming majority is all deposited on soda-lime glass substrate (SLG),
It has been found that the Na atom in substrate can diffuse into film, and then improve the physical property of film.Na diffusion couple Cu2ZnSn
(S1-xSex)4Beneficial effect be mainly reflected in the following [Tejas P.et al., Sol. Energy
Mater.Sol.Cells, 95 (2011), 1001]: 1) Na doping energy enhanced film lattice structure increases film crystallite dimension, drop
Low number of grain boundaries, to efficiently reduce the compound of carrier；2) there are also passivations for Na ion pair film crystal grain, make crystal grain heap
Product more closely, improves film compactness；3) in terms of electric property, the introducing of Na ion, so that Na occupies Cu point and formed
Defect increases number of cavities, significantly improves carrier concentration in film, and then increase film conductivity.Currently, to
Cu2ZnSn(S1-xSex)4Na is introduced in film and mainly passes through three kinds of modes: 1) using soda-lime glass as thin-film solar cells
Substrate material [Guo Q.J.et al., J.Am.Chem.Soc., 132 (2010), 17384]；2) thermal evaporation techniques are used,
One layer of NaF [Li J.V.et al., Appl.Phys.Lett., 102 (2013), 163905] is deposited in film bottom or top；3)
Film is immersed in the solution containing Na ion [Guo Q.et al., Prog. Photovoltaics, 21 (2013), 64].
Above-mentioned Na doping way easily causes the inhomogeneities that Na is adulterated in film, makes to influence to mix there are Na concentration gradient in film
Miscellaneous effect.
Cu2ZnSn(S1-xSex)4The preparation method of film mainly includes liquid phase method [Teodor k.et al., Adv.
Energy Mater., 3 (2013), 34-38], vacuum vapor deposition method [Wang K.et al, Appl.Phys.Lett., 97
(2010), 143508] and magnetron sputtering method [Hironori K.et al., Thin Solid Films, 517 (2009), 2455-
2460].Liquid phase method is unfavorable for sustainable development usually using the stronger organic solvent of a large amount of pollutions, such as toluene, hydrazine；Very
Empty evaporation preparation small area film quality is good, but uniformity of film and element proportion are difficult to ensure when preparing large area film
Controllability, raw material availability and production efficiency are lower, lead to film production higher cost, are unfavorable for large-scale industrial production；
The utilization rate of sputtering method raw material is high, can preferably adjust the stoicheiometry of each element, improves preparation repeatability, is suitble to manufacture
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 side of film
Method, improves the Na uniform doping in film, and weakening even is eliminated Na concentration gradient that may be present in film, further mentions
High Cu2ZnSn(S1-xSex)4Thin-film solar cell photoelectric transfer efficiency.
Summary of the invention
The object of the present invention is to provide a kind of Na to adulterate Cu2ZnSn(S1-xSex)4The preparation method of film.This method can
Na uniform doping in film is improved, the Na doping concentration gradient for even avoiding existing doping way from may cause is weakened, thus
Further increase the performance of thin-film solar cells.
To achieve the above object, the invention adopts the following technical scheme:
A kind of Na doping Cu2ZnSn(S1-xSex)4The preparation method of film, using conventional magnetically controlled sputter method in substrate
Upper preparation Na adulterates Cu2ZnSn(S1-xSex)4(0≤x≤1) film, which comprises the following steps:
1) substrate is cleaned；
2) Cu is prepared in magnetron sputtering2ZnSn(S1-xSex)4Cosputtering NaF or alternatively layered preparation in thin-film process
Cu2ZnSn(S1-xSex)4Film and NaF film；
3) film is heat-treated.
Cu is prepared in magnetron sputtering2ZnSn(S1-xSex)4In thin-film process cosputtering NaF use two ways, that is, continue or
Equal time slots cosputtering NaF.
Wherein, NaF target can individually occupy a target position, with preparation Cu2ZnSn(S1-xSex)4Target one needed for film
Cosputtering is played, cosputtering NaF is using lasting cosputtering mode or waits time slots cosputtering mode.Continuing cosputtering NaF is
Refer to, from preparation Cu2ZnSn(S1-xSex)4Each target as sputter of film starts to sputtering to terminate, and NaF target is in sputtering state always,
That is the sputtering time of NaF and Cu2ZnSn(S1-xSex)4The film preparation time is equal；Equal time slots cosputtering NaF refers to, from system
Standby Cu2ZnSn(S1-xSex)4Each target as sputter of film starts to sputtering to terminate, and NaF target as sputter for a period of time, stops sputtering one
The section time then sputters a period of time again, then stops sputtering a period of time, moves in circles, the time sputtered each time and power
All equal, sputtering time is less than or equal to 30min each time, and the time for stopping sputtering each time is all equal, stops sputtering each time
Time be less than or equal to 15min, and NaF target as sputter number be more than or equal to 2 times.Above two mode is all conducive to improve film
Na uniform doping.
NaF can also be with preparation Cu2ZnSn(S1-xSex)4Composite target material is made in one of target needed for film, continues altogether
Sputter NaF, i.e. NaF sputtering time and preparation Cu2ZnSn(S1-xSex)4The time of film is equal, realizes to Cu2ZnSn(S1- xSex)4The Na of film is adulterated.Wherein, the preparation of composite target material includes two ways: one is in target preparation process, directly
NaF is mixed in target；Another kind is that the consistent NaF small pieces of several sizes are pasted onto a certain target material surface, and composition target is made.
Alternatively layered prepares Cu2ZnSn(S1-xSex)4Film refers to NaF film, in preparation Cu2ZnSn(S1-xSex)4It is thin
In membrane process, NaF is not sputtered, in preparation NaF thin-film process, does not prepare Cu2ZnSn(S1-xSex)4Film, Cu2ZnSn(S1- xSex)4Film replaces preparation with NaF film.In the process, the sputtering number of NaF is more than or equal to 2 times, and single layer NaF film splashes
The time is penetrated less than or equal to 30min, between every two layers of NaF membrane-film preparation process, NaF target stops sputtering time and is less than or equal to 15min.
Film heat treatment can further increase Na uniform doping in film, allow Na further to spread in the film, subtract
It is weak even to be eliminated Na concentration gradient that may be present in film.Film heat treatment link includes the following three types situation: being located at film
In sputter deposition process, i.e., substrate is heated；Alternatively, being located at after thin film sputtering deposition process, i.e., at film subsequent thermal
Reason；Alternatively, having heat treatment in thin film sputtering deposition process and after process.Meanwhile from Cu2ZnSn(S1-xSex)4Film system
Standby angle considers that, to prevent element evaporation in film, film heat treatment temperature is controlled at 600 DEG C or less.Wherein, it is deposited in film
Heat treatment time in the process is equal with film sedimentation time, and the heat treatment time after film deposition process is less than or equal to
2h。
Cu is adulterated using the Na that present patent application the method is finally prepared2ZnSn(S1-xSex)4Film, Na doping mole
Concentration Na/ (Cu+Zn+Sn) is that 0 < Na adulterates molar concentration Na/ (Cu+Zn+Sn)≤3%.
The present invention has the advantages that
In current research, to Cu2ZnSn(S1-xSex)4Film doping Na mainly uses three kinds of modes: 1) using soda-lime glass
Substrate material as film；2) in Cu2ZnSn(S1-xSex)4One layer of NaF is deposited in film bottom or top；3) film is impregnated
In the solution containing Na ion.Above-mentioned doping way easily causes in film there are Na concentration gradient, influences to adulterate effect.
The present invention provides a kind of Na to adulterate Cu2ZnSn(S1-xSex)4The preparation method of film prepares Cu in magnetron sputtering2ZnSn
(S1-xSex)4Cosputtering NaF or alternatively layered prepare Cu in thin-film process2ZnSn(S1-xSex)4Film and NaF film, then
Film is heat-treated, Na uniform doping in film is improved, weakens and even avoids what existing doping way may cause
Na doping concentration gradient, to further increase the performance of thin-film solar cells.
Detailed description of the invention
Fig. 1 is that a kind of Na of the present invention adulterates Cu2ZnSn(S1-xSex)4The preparation method flow chart of film.
Specific embodiment
As shown in Figure 1, a kind of present invention " Na doping Cu2ZnSn(S1-xSex)4The preparation method of film " mainly includes three
A step: 1) substrate is cleaned；2) Cu is prepared in magnetron sputtering2ZnSn(S1-xSex)4In (0≤x≤1) thin-film process altogether
It sputters NaF or alternatively layered prepares Cu2ZnSn(S1-xSex)4Film and NaF film；3) film is heat-treated, including
Three kinds of situations: in thin film sputtering deposition process, substrate is heated；Alternatively, after the completion of thin film sputtering deposition process, it is right
Film carries out subsequent heat treatment；Alternatively, being heat-treated to film in thin film sputtering deposition process and after deposition process.
Implementation of the invention can effectively improve 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 film, NaF target individually occupy one
Target position, in Cu2ZnSnS4(x=0) continue cosputtering NaF in membrane-film preparation process, realize to Cu2ZnSnS4The Na of film mixes
Miscellaneous, film doping concentration is 0.1%, specifically:
Step 1: substrate cleaning:
Sequentially soda lime glass substrates are cleaned by ultrasonic respectively using deionized water, acetone and dehydrated alcohol, when cleaning
Between be 10min, blow the ethyl alcohol of substrate surface remaining off with nitrogen gun.
Step 2: film preparation:
It prepares Na and adulterates Cu2ZnSnS4Film.Target is Cu, ZnS, SnS2And NaF, sputter gas are Ar gas, sputter gas
0.25Pa is pressed, NaF target individually occupies a target position, Na doping is carried out to film by the way of lasting cosputtering NaF,
In, Cu target uses d.c. sputtering mode, ZnS, SnS2Radio-frequency sputtering mode, Cu, ZnS, SnS are used with NaF target2And NaF
The Sputtering power density of target is respectively 0.7W/cm2、4.3W/cm2、1.3W/cm2And 0.3W/cm2, sputtering time 30min.
Step 3: film heat treatment:
After the completion of film preparation, subsequent heat treatment is carried out to film.Film is placed in tube furnace, meanwhile, in tubular type
The quartz boat equipped with S powder is put into furnace quartz ampoule, film heats respectively with quartz boat, with N2As vulcanization carrier gas.It first will be quartzy
Boat is heated to 200 DEG C, stablizes 30min, then to Cu2ZnSnS4Film is heat-treated, and heat treatment temperature is 580 DEG C, when heating
Between 2h.After heating, room temperature, in cooling procedure, N are naturally cooled to2Flow is constant, steady air current.
Embodiment 2
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of film, NaF target individually occupy one
Target position, in Cu2ZnSnSe4(x=1) membrane-film preparation process medium while gap cosputtering NaF is realized to Cu2ZnSnSe4Film
Na doping, film doping concentration be 1.2%, specifically:
Step 1: substrate cleaning:
Sequentially soda lime glass substrates are cleaned by ultrasonic respectively using deionized water, acetone and dehydrated alcohol, when cleaning
Between be 10min, blow the ethyl alcohol of substrate surface remaining off with nitrogen gun.
Step 2: film preparation:
It prepares Na and adulterates Cu2ZnSnSe4Film.Target is Cu, ZnSe, SnSe2And NaF, sputter gas are Ar gas, sputtering
Air pressure 0.5Pa, NaF target individually occupies a target position, using etc. Na carried out to film by the way of the cosputtering NaF of time slots mix
It is miscellaneous, wherein Cu target uses d.c. sputtering mode, ZnSe, SnSe2With NaF target use radio-frequency sputtering mode, Cu, ZnSe,
SnSe2Sputtering power density with NaF target is respectively 0.9W/cm2、4.3W/cm2、1.3W/cm2And 1.4W/cm2, NaF target
Start cosputtering after remaining target as sputter 15min, sputtering time 30min then stops sputtering NaF 15min, then splashes altogether
NaF 30min is penetrated, in the time that NaF target stops sputtering, remaining target still prepares film in cosputtering, in whole process,
NaF cosputtering 2 times, the total sputtering time 90min of film.
Step 3: film heat treatment:
Substrate is heated in membrane-film preparation process, heating temperature is 525 DEG C, heating time and thin film sputtering time
It is equal, it is 30min.
Embodiment 3
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of film, NaF target individually occupy one
Target position, in Cu2ZnSn(S0.6Se0.4)4(x=0.4) membrane-film preparation process medium while gap cosputtering NaF, realization pair
Cu2ZnSn(S0.6Se0.4)4The Na of film is adulterated, and film doping concentration is 3%, specifically:
Step 1: substrate cleaning:
Sequentially soda lime glass substrates are cleaned by ultrasonic respectively using deionized water, acetone and dehydrated alcohol, when cleaning
Between be 10min, blow the ethyl alcohol of substrate surface remaining off with nitrogen gun.
Step 2: film preparation:
It prepares Na and adulterates Cu2ZnSn(S0.6Se0.4)4Film.Target is Cu, ZnS and SnSe2, sputter gas is Ar gas, is splashed
Emanate and press 0.5Pa, NaF target individually occupies a target position, using etc. Na is carried out to film by the way of the cosputtering NaF of time slots
Doping, wherein Cu target uses d.c. sputtering mode, ZnS, SnSe2With NaF target use radio-frequency sputtering mode, Cu, ZnS,
SnSe2Sputtering power density with NaF target is respectively 0.8W/cm2、3.5W/cm2、1.1W/cm2And 3W/cm2, NaF target exists
Start cosputtering after remaining target as sputter 5min, sputtering time 10min then stops sputtering NaF 5min, then cosputtering NaF
10min is recycled 2 times, and in the time that NaF target stops sputtering, remaining target still prepares film in cosputtering, and whole process is splashed
Penetrate time 30min.
Step 3: film heat treatment:
After the completion of film preparation, film is heat-treated.Film is placed in tube furnace, meanwhile, in tubular type hearthstone
The quartz boat equipped with S powder is put into English pipe, film heats respectively with quartz boat, with N2As vulcanization carrier gas.First quartz boat is added
Heat is stablized 30min, is then heat-treated to film to 200 DEG C, and heat treatment temperature is 550 DEG C, heating time 1h.Heating knot
Shu Hou naturally cools to room temperature, in cooling procedure, N2Flow is constant, steady air current.
Embodiment 4
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of film is small by the NaF of same size
Piece, which is pasted on ZnS target, is made ZnS/NaF composition target, in Cu2ZnSnS4(x=0) continue cosputtering in membrane-film preparation process
NaF is realized to Cu2ZnSnS4The Na of film is adulterated, and film doping concentration is 1%, specifically:
Step 1: substrate cleaning:
Sequentially using deionized water, acetone and dehydrated alcohol, soda lime glass substrates are cleaned by ultrasonic respectively, scavenging period
For 10min, the ethyl alcohol of substrate surface remaining is blown off with nitrogen gun.
Step 2: film preparation:
Prepare the Cu of Na doping2ZnSnS4Film.Target is Cu target, ZnS/NaF composite target material and SnS2Target, sputtering
Gas is Ar gas, and NaF small pieces are pasted on ZnS target and composition target is made by sputtering pressure 0.25Pa, continues cosputtering NaF, real
Now the uniform Na of film is adulterated, wherein Cu target uses d.c. sputtering mode, ZnS/NaF composition target and SnS2Target uses
Radio-frequency sputtering mode, Cu target, ZnS/NaF composition target and SnS2The Sputtering power density of target is respectively 0.4W/cm2、2.1W/cm2
And 0.6W/cm2, sputtering time 30min.
Step 3: film heat treatment:
After the completion of film preparation, film is heat-treated.Film is placed in tube furnace, meanwhile, in tubular type hearthstone
The quartz boat equipped with S powder is put into English pipe, film heats respectively with quartz boat, with N2As vulcanization carrier gas.First quartz boat is added
Heat is stablized 30min, is then heat-treated to film to 200 DEG C, and heat treatment temperature is 560 DEG C, heating time 2h.Heating knot
Shu Hou naturally cools to room temperature, in cooling procedure, N2Flow is constant, steady air current.
Embodiment 5
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of film, in ZnS target preparation process
NaF is mixed, ZnS/NaF composite target material is made, and then in Cu2ZnSn(S0.5Se0.5)4(x=0.5) continue in membrane-film preparation process
NaF is sputtered, is realized to Cu2ZnSnS4The Na of film is adulterated, and film doping concentration is 0.5%, specifically:
Step 1: substrate cleaning:
Sequentially soda lime glass substrates are cleaned by ultrasonic respectively using deionized water, acetone and dehydrated alcohol, when cleaning
Between be 10min, blow the ethyl alcohol of substrate surface remaining off with nitrogen gun.
Step 2: film preparation:
It prepares Na and adulterates Cu2ZnSn(S0.5Se0.5)4Film.Target is Cu target, ZnS/NaF composite target material and SnSe2Target
Material, sputter gas are Ar gas, and sputtering pressure 0.5Pa mixes NaF in ZnS target preparation process, ZnS/NaF composition target is made
Material, and then NaF is persistently sputtered in membrane-film preparation process, it realizes and the uniform Na of film is adulterated, wherein Cu target uses direct current
Sputtering mode, ZnS/NaF composition target and SnSe2Target uses radio-frequency sputtering mode, Cu, ZnS/NaF and SnSe2The sputtering function of target
Rate density is respectively 0.7W/cm2、2.8W/cm2And 0.9W/cm2, sputtering time 30min.
Step 3: film heat treatment:
It is heat-treated respectively in membrane-film preparation process and after film preparation.To lining in membrane-film preparation process
Bottom heats 200 DEG C, heating time 30min；After the completion of film preparation, film is placed in tube furnace, meanwhile, in tube furnace
The quartz boat equipped with S powder is put into quartz ampoule, film heats respectively with quartz boat, with N2As vulcanization carrier gas.First by quartz boat
200 DEG C are heated to, stablizes 30min, then film is heat-treated, heat treatment temperature is 550 DEG C, heating time 2h.Heating
After, naturally cool to room temperature, in cooling procedure, N2Flow is constant, steady air current.
Embodiment 6
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of film, is prepared using alternatively layered
Cu2ZnSnS4(x=0) mode of film and NaF film is realized to Cu2ZnSnS4The Na of film is adulterated, and film doping concentration is
2.5%, specifically:
Step 1: substrate cleaning:
Sequentially soda lime glass substrates are cleaned by ultrasonic respectively using deionized water, acetone and dehydrated alcohol, when cleaning
Between be 10min, blow the ethyl alcohol of substrate surface remaining off with nitrogen gun.
Step 2: film preparation:
It prepares Na and adulterates Cu2ZnSnS4Film.Target is Cu, ZnS, SnS2With NaF target, prepared using alternatively layered
Cu2ZnSnS4(x=0) mode of film and NaF film is realized and is adulterated to the Na of film, wherein Cu, ZnS and SnS2Three targets are total
Sputtering preparation Cu2ZnSnS4Film, NaF target individually sputter NaF layers of preparation, and sputter gas is Ar gas, sputtering pressure 0.5Pa, Cu
Target uses d.c. sputtering mode, ZnS target, SnS2Target and NaF target use radio-frequency sputtering mode, Cu target, ZnS target, SnS2Target and
The Sputtering power density of NaF target is respectively 0.9W/cm2、5W/cm2、1.6W/cm2And 1.6W/cm2, in the process, firstly,
Cu, ZnS and SnS2Three target co-sputterings prepare Cu2ZnSnS4Layer 15min, then prepares NaF layers of 30min, alternately with this, always
Sputtering time 90min, wherein Cu, ZnS and SnS2Three target co-sputterings 2 times, NaF target as sputter 2 times.
Step 3: film heat treatment:
After the completion of film preparation, film is heat-treated.Film is placed in tube furnace, meanwhile, in tubular type hearthstone
The quartz boat equipped with S powder is put into English pipe, film heats respectively with quartz boat, with N2As vulcanization carrier gas.First quartz boat is added
Heat is stablized 30min, is then heat-treated to film to 200 DEG C, and heat treatment temperature is 540 DEG C, heating time 2h.Heating knot
Shu Hou naturally cools to room temperature, in cooling procedure, N2Flow is constant, steady air current.
Embodiment 7
A kind of Na doping Cu in the present embodiment2ZnSn(S1-xSex)4The preparation method of film, is prepared using alternatively layered
Cu2ZnSnS4(x=0) mode of film and NaF film is realized to Cu2ZnSnS4The Na of film is adulterated, and film doping concentration is
0.15%, specifically:
Step 1: substrate cleaning:
Sequentially soda lime glass substrates are cleaned by ultrasonic respectively using deionized water, acetone and dehydrated alcohol, when cleaning
Between be 10min, blow the ethyl alcohol of substrate surface remaining off with nitrogen gun.
Step 2: film preparation:
It prepares Na and adulterates Cu2ZnSnS4Film.Target is Cu2ZnSnS4With NaF target, prepared using alternatively layered
Cu2ZnSnS4(x=0) mode of film and NaF film is realized and is adulterated to the Na of film, wherein Cu2ZnSnS4Target preparation
Cu2ZnSnS4Film, NaF target individually sputter NaF layers of preparation, and sputter gas is Ar gas, sputtering pressure 0.25Pa, Cu2ZnSnS4
Target and NaF target are all made of radio-frequency sputtering mode, and Sputtering power density is respectively 3.5W/cm2And 1.1W/cm2, in the process,
Cu is prepared first2ZnSnS4Layer 5min, then prepares NaF layers of 1min, alternately with this, total sputtering time 30min, wherein
Cu2ZnSnS4Target as sputter 5 times, NaF target as sputter 5 times.
Step 3: film heat treatment:
After the completion of film preparation, film is heat-treated.Film is placed in tube furnace, meanwhile, in tubular type hearthstone
The quartz boat equipped with S powder is put into English pipe, film heats respectively with quartz boat, with N2As vulcanization carrier gas.First quartz boat is added
Heat is stablized 30min, is then heat-treated to film to 200 DEG C, and heat treatment temperature is 600 DEG C, heating time 2h.Heating knot
Shu Hou naturally cools to room temperature, in cooling procedure, N2Flow is constant, steady air current.
Claims (3)
1. a kind of Na adulterates Cu2ZnSn(S1-xSex)4The preparation method of film, wherein 0≤x≤1, which is characterized in that using conventional
Magnetically controlled sputter method, comprising the following steps:
1) substrate is cleaned；
2) Cu is prepared in magnetron sputtering2ZnSn(S1-xSex)4In thin-film process using continue or constant duration by the way of cosputtering
NaF；Specifically: NaF target individually occupies a target position, with preparation Cu2ZnSn(S1-xSex)4Target needed for film splashes altogether together
It penetrates, according to lasting cosputtering NaF mode, the sputtering time and Cu of NaF2ZnSn(S1-xSex)4The film preparation time is equal；If
Using etc. time slots cosputtering NaF mode, NaF target as sputter number be more than or equal to 2 times, the NaF target single cosputtering time
Less than or equal to 30min, per cosputtering NaF interprocedual twice, NaF target stops sputtering time and is less than or equal to 15min；Alternatively, will
NaF and preparation Cu2ZnSn(S1-xSex)4Composite target material is made in one of target needed for film, continues cosputtering NaF, realization pair
Cu2ZnSn(S1-xSex)4The Na of film is adulterated, and NaF target continues cosputtering time and Cu2ZnSn(S1-xSex)4When film preparation
Between it is equal；
3) film is heat-treated.
2. a kind of Na according to claim 1 adulterates Cu2ZnSn(S1-xSex)4The preparation method of film, it is characterised in that:
Film heat treatment link includes the following three types situation: being located in thin film sputtering deposition process, i.e., heats to substrate；Alternatively,
After thin film sputtering deposition process, i.e. film subsequent heat treatment；Alternatively, in thin film sputtering deposition process and after process
There is heat treatment；Film heat treatment temperature is less than or equal to 600 DEG C；Wherein, the heat treatment time in film deposition process with it is thin
Film sedimentation time is equal, and the heat treatment time after film deposition process is less than or equal to 2h.
3. a kind of Na according to claim 1 adulterates Cu2ZnSn(S1-xSex)4The preparation method of film, it is characterised in that:
The Na doping Cu being finally prepared2ZnSn(S1-xSex)4In film, Na doping molar concentration Na/ (Cu+Zn+Sn) is that 0 < Na mixes
Miscellaneous molar concentration Na/ (Cu+Zn+Sn)≤3%.
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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