CN109841696A - Modified copper-zinc-tin-sulfur film, preparation method and solar battery - Google Patents
Modified copper-zinc-tin-sulfur film, preparation method and solar battery Download PDFInfo
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- CN109841696A CN109841696A CN201910209454.2A CN201910209454A CN109841696A CN 109841696 A CN109841696 A CN 109841696A CN 201910209454 A CN201910209454 A CN 201910209454A CN 109841696 A CN109841696 A CN 109841696A
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Abstract
A kind of preparation method of the copper-zinc-tin-sulfur film of modification, comprising steps of the copper-zinc-tin-sulfur precursor solution that configuration is modified: the ratio of each component is in the copper-zinc-tin-sulfur precursor solution of the modification: the ratio of the quality sum of the quality and zinc-tin element of copper is 0.9-1, the quality of Zn-ef ficiency and the mass values of tin element are 0.9-1.3, the ratio of the quality sum of the quality and copper zinc-tin element of element sulphur is 2-2.1, and the ratio of the quality sum of the quality and zinc-iron element of ferro element is 0-1；On the base layer by the copper-zinc-tin-sulfur precursor solution spin coating of the modification；The pre-heat treatment is carried out to the copper-zinc-tin-sulfur precursor solution for the modification being spin-coated on the basal layer, obtains modified copper-zinc-tin-sulfur membrane sample；And vulcanization annealing is carried out to the copper-zinc-tin-sulfur film sample of the modification, to obtain the copper-zinc-tin-sulfur film of the modification.The invention further relates to a kind of copper-zinc-tin-sulfur film of modification and solar batteries.
Description
Technical field
The present invention relates to technical field of solar batteries more particularly to the copper of a kind of copper-zinc-tin-sulfur film of modification, modification
The preparation method and solar battery of zinc-tin-sulfur film.
Background technique
Copper-zinc-tin-sulfur (copper zinc tin sulfur, copper-zinc-tin-sulfur) thin-film material have much with current demand
With the advantages of, show one's talent in numerous solar cell materials.Copper-zinc-tin-sulfur film material is direct band-gap semicondictor, is led
Electric type is p-type, and forbidden bandwidth is 1.5eV or so, and absorptivity is very high.In addition, the price of composition copper-zinc-tin-sulfur film element
It is very cheap and nontoxic and pollution-free.Therefore, copper-zinc-tin-sulfur film material has great potentiality on photovoltaic device.
In the prior art, copper-zinc-tin-sulfur film is prepared frequently with sol-gal process, however, being made by sol-gal process
Copper-zinc-tin-sulfur film crystal grain it is very tiny, and defect and impurity phase is easy to produce, to cause the knot of copper-zinc-tin-sulfur film
The problems such as brilliant poor quality, lower cell performance, so as to cause the photoelectricity of the solar battery of the application copper-zinc-tin-sulfur film
Transformation efficiency is not high.
Summary of the invention
In view of this, the present invention provides the copper-zinc-tin-sulfur film that a kind of crystalline quality is good, battery performance is high.
It there is a need to provide a kind of preparation method for the copper-zinc-tin-sulfur film that crystalline quality is good, battery performance is high.
It there is a need to provide a kind of solar battery that incident photon-to-electron conversion efficiency is high.
A kind of copper-zinc-tin-sulfur film of modification changes doped with Fe element in the copper-zinc-tin-sulfur film of the modification described
Property copper-zinc-tin-sulfur film in, the ratio of the quality sum of the quality and zinc-iron element of ferro element is 0-1.
Further, it the ratio of each component is in the copper-zinc-tin-sulfur film of the modification: the quality and zinc-tin of copper
The ratio of the quality sum of element is 0.9-1, and the quality of Zn-ef ficiency and the mass values of tin element are 0.9-1.3, element sulphur
The ratio of quality and the quality sum of copper zinc-tin element is 2-2.1.
A kind of preparation method of the copper-zinc-tin-sulfur film of modification, comprising steps of the copper-zinc-tin-sulfur presoma of configuration modification is molten
Liquid: the ratio of each component is in the copper-zinc-tin-sulfur precursor solution of the modification: the quality of copper and the matter of zinc-tin element
The ratio of the sum of amount is 0.9-1, and the quality of Zn-ef ficiency and the mass values of tin element are 0.9-1.3, the quality and copper of element sulphur
The ratio of the quality sum of zinc-tin element is 2-2.1, and the ratio of the quality sum of the quality and zinc-iron element of ferro element is 0-1；
On the base layer by the copper-zinc-tin-sulfur precursor solution spin coating of the modification；To the modification being spin-coated on the basal layer
Copper-zinc-tin-sulfur precursor solution carries out the pre-heat treatment, obtains modified copper-zinc-tin-sulfur membrane sample；And the copper zinc-tin to the modification
Sulphur film sample carries out vulcanization annealing, to obtain the copper-zinc-tin-sulfur film of the modification.
Further, the temperature of the pre-heat treatment is 300 degrees Celsius, and preheating time is 2 minutes.
Further, the spin coating includes first carrying out low speed spin coating, and rear to carry out high speed spin coating, the speed of low speed spin coating is
800 revs/min, the speed of high speed spin coating is 3000 revs/min of spin speed.
Further, the time of the low speed spin coating is 6 seconds, and the time of the high speed spin coating is 24 seconds.
Further, the step of carrying out vulcanization annealing before, the pre-heat treatment and the spin coating are alternately.
Further, the vulcanization annealing is comprising steps of sulphur powder and the copper-zinc-tin-sulfur film sample of the modification are distinguished
It is placed in the same tube furnace；And it anneals under vacuum and argon atmosphere.
Further, the technological parameter of the annealing are as follows: annealing temperature is 580 DEG C, and annealing soaking time is 1 hour, is moved back
Fire partial pressure is 0.15bar.
A kind of solar battery, the solar battery include a basal layer, a back electrode being formed on the substrate
The copper-zinc-tin-sulfur film that layer, the copper-zinc-tin-sulfur film of a modification being formed on the back electrode layer, one are formed in the modification
On buffer layer, one be formed on the buffer layer intrinsic zinc oxide Window layer, be formed in the intrinsic zinc oxide Window layer
On tin indium oxide Window layer and the top electrode that is formed in the tin indium oxide Window layer, the copper-zinc-tin-sulfur film of the modification
It is prepared by the preparation method for the copper-zinc-tin-sulfur film being modified as described above.
Copper-zinc-tin-sulfur film, preparation method and the solar battery of modification provided by the invention, in modified copper zinc-tin
The copper-zinc-tin-sulfur film being modified doped with a small amount of Fe element in sulphur film and using the method optimizing of vulcanization annealing, can not only be more
The surface topography and photoelectric properties of the modified copper-zinc-tin-sulfur film of good promotion, moreover it is possible to promote the knot of modified copper-zinc-tin-sulfur film
Crystalloid amount.In addition, having using the solar battery that the copper-zinc-tin-sulfur film of the modification doped with a small amount of Fe element assembles higher
Photoelectric conversion efficiency.
Detailed description of the invention
Fig. 1 is the cross-sectional view for the solar battery that an embodiment of the present invention provides.
Fig. 2 is the preparation flow figure for the solar battery that an embodiment of the present invention provides.
Fig. 3 is the preparation flow figure of the copper-zinc-tin-sulfur film for the modification that an embodiment of the present invention provides.
Fig. 4 is the shape appearance figure of the copper-zinc-tin-sulfur film of the modification of vulcanization annealing front and back.
Fig. 5 be vulcanization annealing front and back modification copper-zinc-tin-sulfur film X-ray diffraction (X-raydiffraction,
XRD) figure.
Fig. 6 is the Raman spectrogram of the copper-zinc-tin-sulfur film of the modification of vulcanization annealing front and back.
Fig. 7 is the shape appearance figure for being doped with the copper-zinc-tin-sulfur film of the modification after different content Fe；Wherein, a) undoped with Fe；
B) ratio of the quality sum of the quality and zinc-iron element of the ferro element adulterated is 0.2；C) quality and zinc of the ferro element adulterated
The ratio of the quality sum of ferro element is 0.4；D) ratio of the quality and the quality sum of zinc-iron element of the ferro element adulterated is
0.6；E) ratio of the quality sum of the quality and zinc-iron element of the ferro element adulterated is 0.8；F) quality of the ferro element adulterated
Ratio with the quality sum of zinc-iron element is 1.0.
Fig. 8 is the change in resistance curve for being doped with the copper-zinc-tin-sulfur film of the modification after different content Fe.
Fig. 9 is the dark current curve of modified copper-zinc-tin-sulfur film as made from Examples 1 and 2.
Figure 10 is the photocurrent curve of modified copper-zinc-tin-sulfur film as made from Examples 1 and 2.
Figure 11 is the VA characteristic curve figure of modified copper-zinc-tin-sulfur film as made from embodiment 2.
Main element symbol description
Solar battery 100
Basal layer 10
Back electrode layer 20
Modified copper-zinc-tin-sulfur film 30
Buffer layer 40
Intrinsic zinc oxide Window layer 50
Tin indium oxide Window layer 60
Top electrode 70
The present invention that the following detailed description will be further explained with reference to the above drawings.
Specific embodiment
For can the present invention is further explained reaches the technical means and efficacy that predetermined goal of the invention taken, below in conjunction with figure
1-11 and better embodiment, to the specific reality of copper-zinc-tin-sulfur film provided by the invention, preparation method and solar battery
Mode, structure, feature and its effect are applied, is made as described in detail below.
Referring to Fig. 1, the present invention provides a kind of solar battery 100, the solar battery 100 includes a basal layer
10, a back electrode layer 20, one being formed on the basal layer 10 is formed in the copper zinc-tin of the modification on the back electrode layer 20
The buffer layer 40, one that sulphur film 30, one is formed on the copper-zinc-tin-sulfur film 30 of the modification is formed on the buffer layer 40
Intrinsic zinc oxide Window layer 50, tin indium oxide (the indium tin that is formed in the intrinsic zinc oxide Window layer 50
Oxid, ITO) Window layer 60 and the top electrode 70 that is formed in the tin indium oxide Window layer 60.
In the present embodiment, the basal layer 10 is soda-lime glass basal layer.The basal layer 10 is the solar energy
Battery 100 provides a supporting role.
In the present embodiment, the back electrode layer 20 is molybdenum back electrode layer.Wherein, the back electrode layer 20 it is described too
Closed circuit is formed as anode in positive energy battery 100 and with outside.The back electrode layer 20 with a thickness of 280-320.It is preferred that
Ground, the back electrode layer 20 with a thickness of 300nm.
Wherein, p-type light absorbing layer of the copper-zinc-tin-sulfur film 30 of the modification as the solar battery 100.Wherein,
Doped with Fe in the copper-zinc-tin-sulfur film 30 of the modification, the ratio of each component is in the copper-zinc-tin-sulfur precursor solution:
The ratio of the quality sum of the quality and zinc-tin element of copper is 0.9-1, the quality of Zn-ef ficiency and the mass values of tin element
For 0.9-1.3, the ratio of the quality sum of the quality and copper zinc-tin element of element sulphur is 2-2.1, the quality and zinc-iron of ferro element
The ratio of the quality sum of element is 0-1.Preferably, it the ratio of each component is in the copper-zinc-tin-sulfur film 30 of the modification: copper
The ratio of the quality sum of the quality and zinc-tin element of element is 1, and the quality of Zn-ef ficiency and the mass values of tin element are 1.2,
The ratio of the quality sum of the quality and copper zinc-tin element of element sulphur is 2, the quality of ferro element and the quality sum of zinc-iron element
Ratio be 0.2.The copper-zinc-tin-sulfur film 30 of the modification with a thickness of 0.8-1.5 μm.
In the present embodiment, the buffer layer 40 is CeS buffer layer.Wherein, the CeS buffer layer is described for alleviating
Forbidden bandwidth differs too big problem when modified copper-zinc-tin-sulfur film 30 forms PN junction with the intrinsic zinc oxide Window layer 50,
CdS and 30 lattice match of copper-zinc-tin-sulfur film of the modification are good, can form second type hetero-junctions, can transport light well
Raw carrier.The buffer layer 40 with a thickness of 50-90.Preferably, the buffer layer 40 with a thickness of 80nm.
Wherein, PN junction is formed between the intrinsic zinc oxide Window layer 50 and the copper-zinc-tin-sulfur film 30 of the modification.Institute
State intrinsic zinc oxide Window layer 50 with a thickness of 50-65.Preferably, the intrinsic zinc oxide Window layer 50 with a thickness of 60nm.
Wherein, the tin indium oxide Window layer 60 with a thickness of 190-205.Preferably, the tin indium oxide Window layer 60
With a thickness of 200nm.
In the present embodiment, the top electrode 70 is Ag electrode.Wherein, the top electrode 70 is for collecting the oxidation
The carrier that indium tin Window layer 60 transports is simultaneously the cathode of battery with external circuit electrical connection.Wherein, the top electrode 70
With a thickness of 270-340, having a size of 3 × 3-6 × 6.Preferably, the top electrode 70 with a thickness of 300nm, having a size of 5 × 5mm2。
The present invention also provides a kind of copper-zinc-tin-sulfur film 30 of modification, described in the copper-zinc-tin-sulfur film 30 of the modification is used as
The p-type light absorbing layer of solar battery 100.Wherein, in the copper-zinc-tin-sulfur film 30 of the modification doped with Fe, the modification
The ratio of each component is in copper-zinc-tin-sulfur film 30: the ratio of the quality sum of the quality and zinc-tin element of copper is 0.9-1,
The quality of Zn-ef ficiency and the mass values of tin element are 0.9-1.3, the quality sum of the quality and copper zinc-tin element of element sulphur
Ratio is 2-2.1, and the ratio of the quality sum of the quality and zinc-iron element of ferro element is 0-1.Preferably, the copper zinc of the modification
The ratio of each component is in tin sulphur film 30: the ratio of the quality sum of the quality and zinc-tin element of copper is 1, Zn-ef ficiency
The mass values of quality and tin element are 1.2, and the ratio of the quality sum of the quality and copper zinc-tin element of element sulphur is 2, iron member
The ratio of the quality sum of the quality and zinc-iron element of element is 0.2.The copper-zinc-tin-sulfur film 30 of the modification with a thickness of 0.8-
1.5μm。
Fig. 2-3 is please referred to, the present invention also provides a kind of preparation methods of solar battery 100, include the following steps:
Step S1 provides a basal layer 10, and cleans to the basal layer 10.
Wherein, the basal layer 10 is soda-lime glass basal layer.
Wherein, clean the method for the basal layer 10 comprising steps of
The first step cleans the basal layer 10 three to five times with cleanser and diluted glass cleaner, described in removal
Most impurity and grease on basal layer 10 guarantee that water energy is enough and flow in 10 Smooth of basal layer.
Second step, the successively ultrasound 15min in isopropanol, acetone by the basal layer 10 after above-mentioned cleaning, with removal
Remaining dust, grease etc..
The basal layer 10 after ultrasound is put into ultrasound 15min in dehydrated alcohol, to remove remaining isopropyl by third step
Pure and mild acetone.
4th step, the basal layer 10 after third step is cleaned are put into spare in baking box with being dried with nitrogen.
Wherein, cleaning the basal layer 10 can reduce the wind of the film separation and cracking that are formed on the basal layer 10
Danger.
Step S2 forms a back electrode layer 20 on the basal layer 10.
Wherein, closure is formed as the effect of anode in solar battery 100 described in the back electrode layer 20 and with outside
Circuit.
In the present embodiment, the back electrode layer 20 is molybdenum back electrode layer.
In the present embodiment, the back electrode layer 20 is formed by magnetron sputtering method.Wherein, sputtering pressure 1Pa splashes
Penetrating power is 80W, sputtering time 30min.
Wherein, the back electrode layer 20 with a thickness of 270-330.Preferably, the back electrode layer 20 with a thickness of
300nm。
Step S3 forms modified copper-zinc-tin-sulfur film 30 on the back electrode layer 20.
In the present embodiment, doped with Fe, the copper-zinc-tin-sulfur of the modification in the copper-zinc-tin-sulfur film 30 of the modification
The ratio of each component is in film 30: the ratio of the quality sum of the quality and zinc-tin element of copper is 0.9-1, Zn-ef ficiency
The mass values of quality and tin element are 0.9-1.3, and the ratio of the quality sum of the quality and copper zinc-tin element of element sulphur is 2-
2.1, the ratio of the quality sum of the quality and zinc-iron element of ferro element is 0-1.Preferably, the copper-zinc-tin-sulfur film of the modification
The ratio of each component is in 30: the ratio of the quality sum of the quality and zinc-tin element of copper is 1, the quality and tin of Zn-ef ficiency
The mass values of element are 1.2, and the ratio of the quality sum of the quality and copper zinc-tin element of element sulphur is 2, the quality of ferro element
Ratio with the quality sum of zinc-iron element is 0.2.The copper-zinc-tin-sulfur film 30 of the modification with a thickness of 0.8-1.5 μm.
In the present embodiment, referring to Fig. 3, the copper-zinc-tin-sulfur film 30 for preparing the modification specifically includes following step
It is rapid:
Step S31 configures copper-zinc-tin-sulfur precursor solution using sol-gal process.
Wherein, the ratio of each component is in the copper-zinc-tin-sulfur precursor solution: the quality and zinc-tin element of copper
The ratio of quality sum be 0.9-1, the mass values of the quality of Zn-ef ficiency and tin element are 0.9-1.3, the quality of element sulphur
Ratio with the quality sum of copper zinc-tin element is 2-2.1, and the ratio of the quality and the quality sum of zinc-iron element of ferro element is
0-1.Preferably, it the ratio of each component is in the copper-zinc-tin-sulfur film 30 of the modification: the quality of copper and zinc-tin element
The ratio of quality sum is 1, and the quality of Zn-ef ficiency and the mass values of tin element are 1.2, quality and copper the zinc-tin member of element sulphur
The ratio of the quality sum of element is 2, and the ratio of the quality sum of the quality and zinc-iron element of ferro element is 0.2.
Specifically, the step of configuring the copper-zinc-tin-sulfur precursor solution includes: that oil bath pan is raised to 43 DEG C and is kept the temperature, and is claimed
Amount 20ml ethylene glycol monomethyl ether solution be placed in clean beaker for use, then weighing 2.436g thiocarbamide, 1.054g zinc acetate,
1.406g copper acetate, 0.907g stannous chloride and 0.463g FeSO4·7H2O, and be sequentially placed into solvent-laden beaker,
It is quickly transferred to carry out magnetic agitation in oil bath pan, mixing time is 30 minutes, and mixing speed is 15 turns/min.Later, it takes out
5 drop triethanolamine stabilizers and magnetic agitation 10 minutes are added dropwise at normal temperature, is then filtered, obtains to solution for beaker
The bright orange-red copper-zinc-tin-sulfur precursor solution of clarification.
The copper-zinc-tin-sulfur precursor solution is spin-coated on the back electrode layer 20 by step S32.
Specifically, spin coating the specific process steps are as follows: the first step, the basal layer 10 cleaned up (has been formed into back electricity
20) pole layer is placed on spin coater；Second step drips upper precursor solution on basal layer 10, it is preferable that primary drop 3-4 drop forerunner
Liquid solution；Third step starts spin coating, first low speed spin coating 6s, 800 turns/min of spin speed, then high speed spin coating 24s, spin speed
3000 turns/min.
Step S33, the pre-heat treatment are spin-coated on the copper-zinc-tin-sulfur precursor solution on the back electrode layer 20, obtain copper
Zinc-tin-sulfur film sample.
Specifically, the pre-heat treatment the specific process steps are as follows: copper-zinc-tin-sulfur film sample is placed on warm table, heat
Platform temperature is 300 DEG C, preheating time 2min.Then sample is removed, placement cools down in air.Later, continue spin coating and pre-
Heat treatment repeats 9 times above process, obtains the copper-zinc-tin-sulfur film of about 1.20 μ m-thicks.Wherein, time of spin coating and preheating is repeated
Number, preheating temperature and preheating time are not limited to above-mentioned repetition pass, preheating temperature and preheating time.
Step S34 carries out vulcanization annealing to the copper-zinc-tin-sulfur film product.
In the present embodiment, the sulphur source that vulcanization annealing needs is sulphur powder, and in other embodiments, vulcanization annealing needs
Sulphur source can also be other safe and cheap sulfide.
Specifically, the concrete technology of the vulcanization annealing is comprising steps of firstly, 2g sulphur powder is put into quartz boat, sulphur powder
It is placed in the tube furnace left side, sample is placed in the right；Secondly, leading to using mechanical pump by the tubular type stove evacuation 3 times into tube furnace
Enter argon gas, and adjusts operating air pressure；Again, the parameter and annealing of input service.The parameter and annealing are as follows: annealing temperature
When 580 DEG C, annealing soaking time be 1 hour, annealing partial pressure be 0.15bar.Wherein, the quality of the sulphur powder and sulphur powder are in tubular type
Position in furnace is not limited thereto.
Wherein, the annealing process is the recovery and recrystallization process of copper-zinc-tin-sulfur film, particularly significant to quality of forming film.?
Under 580 DEG C of annealing temperature, following decomposition reaction is had occurred in copper-zinc-tin-sulfur:
Cu2ZnSnS4→Cu2S+ZnS+SnS+S
Since the saturated vapour pressure of SnS and S are excessively high, at high temperature, SnS and S can volatilize, so that it is thin to reduce copper-zinc-tin-sulfur
The content of Sn and S in film.The loss of Sn and S will form deep energy level defect, V in the very thin film of copper-zinc-tin-sulfurSnVacancy and VSVacancy, shape
At the recombination region of carrier, finally influences the separation of carrier and transport.Therefore, it is annealed using vulcanization, above-mentionedization can be inhibited
The chemical balance for learning decomposition reaction moves right, and reduces the loss of Sn and S element in copper-zinc-tin-sulfur film, thus guarantee to be formed
The crystalline quality of copper-zinc-tin-sulfur film.
Step S4 forms one on the surface far from the back electrode layer 20 of the copper-zinc-tin-sulfur film 30 of the modification and delays
Rush layer 40.
In the present embodiment, the buffer layer 40 is CdS buffer layer.The CdS buffer layer is for alleviating the modification
Copper-zinc-tin-sulfur film 30 and the intrinsic zinc oxide Window layer 50 when forming PN junction forbidden bandwidth differ too big problem, CdS
It is good with 30 lattice match of copper-zinc-tin-sulfur film of the modification, second type hetero-junctions can be formed, photoproduction can be transported well
Carrier.
In the present embodiment, the CdS buffer layer is prepared using immersion method, comprising steps of
Water bath temperature is risen to 70 DEG C and keeps constant temperature by the first step.
Second step configures the thiourea solution of 1.6M and places it in spare in a conical flask.
Third step configures the CdSO of 0.04M4Solution simultaneously places it in spare in another conical flask.
4th step takes the CdSO of 20ml with pipette4Solution, 30ml ammonium hydroxide, 20ml thiourea solution and 120ml deionized water
It is sequentially placed into the beaker of 200ml.
5th step places the beaker rapidly in 70 DEG C of water-bath, then the copper-zinc-tin-sulfur film 30 of the modification (is had
Basal layer 10 and back electrode layer 20) it is deposited in the beaker in the water-bath, sedimentation time is 40min or so.
6th step takes out the copper-zinc-tin-sulfur film, rinses the copper-zinc-tin-sulfur film table with deionized water at room temperature
Face, to remove the impurity of film surface adherency.
Sample is placed in 100 DEG C of drying box and dries by the 7th step.Wherein, what film surface was formed is in lurid
Film layer is CdS buffer layer.In the present embodiment, the CdS buffer layer 40 with a thickness of 80nm.
Step S5 forms an intrinsic zinc oxide Window layer 50 on the buffer layer 40.
Wherein, PN junction is formed between the intrinsic zinc oxide Window layer 50 and the copper-zinc-tin-sulfur film 30 of the modification.
In the present embodiment, using ZnO target material, and the intrinsic zinc oxide Window layer is formed using magnetron sputtering method
50.Wherein, sputtering pressure 1.2Pa, sputtering power 70W, sputtering time 25min.The native oxide being consequently formed
Zinc Window layer 50 with a thickness of 60nm.
Step S6 forms a tin indium oxide Window layer 60 in the intrinsic zinc oxide Window layer 50.
In the present embodiment, using tin indium oxide target material, and the tin indium oxide window is formed using magnetron sputtering method
Mouth layer 60.Wherein, sputtering pressure 0.3Pa, sputtering power 80W, sputtering time 10min.The oxidation being consequently formed
Indium tin Window layer 60 with a thickness of 200nm.
Step S7 forms top electrode 70, in the tin indium oxide Window layer 60 to form solar battery 100.
In the present embodiment, the top electrode 70 is Ag electrode.Wherein, the top electrode 70 is for collecting the oxidation
The carrier that indium tin Window layer 60 transports is simultaneously the cathode of battery with external circuit electrical connection.
In the present embodiment, Ag electrode, good conductivity, high mechanical strength are prepared using thermal evaporation.In this implementation
In mode, the top electrode 70 with a thickness of 300nm having a size of 5 × 5mm2。
The present invention will be specifically described by specific embodiment and comparative example below.
Embodiment 1
Configuration copper-zinc-tin-sulfur precursor solution: being raised to 43 DEG C for oil bath pan and keep the temperature, and weighs 20ml ethylene glycol monomethyl ether solution
Stand-by, then weighing 2.436g thiocarbamide, 1.054g zinc acetate, 1.406g copper acetate and 0.907g chlorination is placed in clean beaker
Stannous and 0.463g FeSO4·7H2O is sequentially placed into solvent-laden beaker, and is quickly transferred to progress magnetic force in oil bath pan and is stirred
It mixes, mixing time is 30 minutes, and mixing speed is 15 turns/min.After 30 minutes to be mixed, beaker is taken out, 5 are added dropwise at normal temperature
Triethanolamine stabilizer and magnetic agitation 10 minutes are dripped, then solution is filtered, obtain the transparent orange-red copper zinc of clarification
Tin sulphur precursor solution.
The copper-zinc-tin-sulfur precursor solution is spin-coated in a clean soda-lime glass substrate and (is formed with Mo back in substrate
Electrode layer, the copper-zinc-tin-sulfur precursor solution are spin-coated on Mo back electrode layer): the 10 (shape of basal layer that will be cleaned up
At back electrode layer 20) it is placed on spin coater, 3-4 drop precursor solution in drop, start spin coating, first low speed spin coating 6s, spin speed
800 turns/min, then high speed spin coating 24s, 3000 turns/min of spin speed.
The copper-zinc-tin-sulfur precursor solution of the pre-heat treatment spin coating, obtains copper-zinc-tin-sulfur film sample: will after spin coating is complete
Copper-zinc-tin-sulfur film sample is placed on warm table, and heating platen temperature is 300 DEG C, preheating time 2min；Then, copper-zinc-tin-sulfur is removed
Film sample, placement cool down in air；Later, alternately spin coating and the pre-heat treatment, it is 9 times that heat treatment, which repeats pass, is obtained
To the copper-zinc-tin-sulfur film sample of about 1.20 μ m-thicks.
Vulcanization annealing: 2g sulphur powder is put into quartz boat, and sulphur powder is placed in the tube furnace left side, and sample is placed in the right；Use machine
Tool is pumped the tubular type stove evacuation 3 times, argon gas is passed through into tube furnace, and adjust operating air pressure；The lehr attendant of input service
Skill parameter.The parameter and annealing are as follows: 580 DEG C when annealing temperature, annealing soaking time is 1 hour, and annealing partial pressure is
0.15bar.Wherein, Fe content: Fe/ (Fe+Zn)=0.2.
Embodiment 2
Embodiment 2 the difference from embodiment 1 is that, the FeSO being added into the copper-zinc-tin-sulfur precursor solution4·7H2O
Quality be 1.233g, wherein Fe content: Fe/ (Fe+Zn)=0.4.
Embodiment 3
Embodiment 3 the difference from embodiment 1 is that, the FeSO being added into the copper-zinc-tin-sulfur precursor solution4·7H2O
Quality be 2.777g, wherein Fe content: Fe/ (Fe+Zn)=0.6.
Embodiment 4
Embodiment 4 the difference from embodiment 1 is that, the FeSO being added into the copper-zinc-tin-sulfur precursor solution4·7H2O
Quality be 7.406g, wherein Fe content: Fe/ (Fe+Zn)=0.8.
Embodiment 5
Embodiment 5 the difference from embodiment 1 is that, the FeSO being added into the copper-zinc-tin-sulfur precursor solution4·7H2O
Quality be 1.596g, and without zinc acetate.Wherein, Fe content: Fe/ (Fe+Zn)=1.0.
Comparative example 1
Comparative example 1 the difference from embodiment 1 is that, do not include Fe element in the copper-zinc-tin-sulfur precursor solution, wherein
Fe content: Fe/ (Fe+Zn)=0.0.
Utilize the surface shape of the copper-zinc-tin-sulfur film of vulcanization annealing front and back in scanning electron microscope observation comparative example 1
Looks are shown in Fig. 4.Wherein, the surface topography map of the copper-zinc-tin-sulfur film before a) annealing for vulcanization in embodiment 1；B) in embodiment 1
The surface topography map of the copper-zinc-tin-sulfur film obtained after vulcanization annealing.
Using the copper-zinc-tin-sulfur film of vulcanization annealing front and back in X-ray diffractometer characterization comparative example 1, Fig. 5 is seen.
Using the copper-zinc-tin-sulfur film of vulcanization annealing front and back in Raman spectrum analysis instrument sign comparative example 1, Fig. 6 is seen.
Copper-zinc-tin-sulfur film made from embodiment 1-5 and comparative example 1 is observed using scanning electron microscope, sees Fig. 7.
The square resistance for the copper-zinc-tin-sulfur film that embodiment 1-5 and comparative example 1 obtain is measured using four probe resistance instrument, and
Resistivity is calculated, change in resistance curve is made according to resistivity, sees Fig. 8.
The brightness electric current for the copper-zinc-tin-sulfur film that testing example 1-5 and comparative example 1 obtain, is shown in Fig. 9-10.
Solar battery is assembled using copper-zinc-tin-sulfur film made from embodiment 1, and the volt-ampere for testing solar battery is special
Linearity curve is shown in Figure 11.
Wherein, as shown in Figure 4, the copper-zinc-tin-sulfur film crystal grain very little for not carrying out vulcanization annealing, can say almost without pattern,
It is easy to appear many defects such as: cavity, slight crack.There is also many non-volatile carbon impurities, chlorine in copper-zinc-tin-sulfur film at this time
The residual such as compound.After vulcanization annealing, copper-zinc-tin-sulfur has carried out recovery and recrystallization process, and crystal grain is grown up rapidly, and cavity and crackle disappear
It loses, impurity volatilization, the crystal grain on surface becomes very fine and close, uniform.
Wherein, as shown in Figure 5, there is diffraction maximum in certain angles of diffraction in the copper-zinc-tin-sulfur film before and after annealing, for not
The copper-zinc-tin-sulfur film for vulcanizing annealing, it is found that its orientation is unobvious, only has a small peak in 28.5 ° of corresponding (112) crystal orientation, and
There is miscellaneous peak in other angles of diffraction.Copper-zinc-tin-sulfur crystal diffraction peak after comparison discovery vulcanization annealing is fairly obvious, and along (112)
The diffraction maximum of crystal orientation preferred orientation, miscellaneous peak is unobvious.
It will be appreciated from fig. 6 that annealing front and back, copper-zinc-tin-sulfur film is in 328cm-1The A1 mode vibration that copper-zinc-tin-sulfur occurs in place is drawn
Graceful characteristic peak.The Raman peak intensity of copper-zinc-tin-sulfur film is lower before annealing, and the value of a half width of Raman peaks is very big, illustrates crystallization
Quality is simultaneously bad, and the crystal grain of film is smaller.The Raman peaks for belonging to copper-zinc-tin-sulfur film after annealing are very strong, and halfwidth is very narrow, and
Without other miscellaneous peaks, illustrate that film crystalline quality gets a promotion.
It is analyzed by above-mentioned XRD and Raman, has critically important work to copper-zinc-tin-sulfur film crystalline quality using vulcanization annealing
With.Copper-zinc-tin-sulfur film sample stability after annealing is very strong.
Wherein, as shown in Figure 7, as preceding copper-zinc-tin-sulfur drives the increase of Fe content in liquid solution, the quantity of big crystal grain becomes more,
Crystallite dimension becomes larger, last to reduce again.Illustrate that the incorporation of appropriate Fe has the crystal grain of copper-zinc-tin-sulfur film and promotes growth
Effect.But too many Fe can reduce the size of crystal grain again, and introduce a large amount of defects.When Fe content is 0.2, copper-zinc-tin-sulfur film
Pattern is best, and copper-zinc-tin-sulfur film is very fine and close, uniform at this time, and the defects of without hole and crackle, grain surface is smooth, film
Surface smoothness is very high, and average grain size is maximum, and there are many big crystal grain quantity.
Wherein, as shown in Figure 8, the resistivity of copper-zinc-tin-sulfur film first reduces with the increase of doped element Fe content and increases afterwards
Add.When doped element Fe content is 0.2, the resistivity of copper-zinc-tin-sulfur film is reduced to 10-3The order of magnitude, significant increase copper zinc
The electric property of tin sulphur film.
Wherein, by Fig. 9-10 it is found that gained highest dark current is 10 under dark state-3The order of magnitude, and adulterate Fe content and be
Dark current when dark current when 0.2 is greater than undoped with Fe.Under light state, highest photoelectric current when doping Fe content is 0.2 exists
100The order of magnitude, and photoelectric current when its photoelectric current is greater than undoped with Fe；And as bias increases, photoelectric current is increased with it.Comparison
The size of photoelectric current and dark current illustrates to adulterate the copper-zinc-tin-sulfur film obtained when Fe content is 0.2 with photoelectric characteristic, and by
In introducing illumination, the dramatic promotion of conductance property for the copper-zinc-tin-sulfur film that doping Fe content obtains when being 0.2 contains wherein adulterating Fe
The Light To Dark Ratio for the copper-zinc-tin-sulfur film that amount obtains when being 0.2 has averagely reached 104The order of magnitude.Therefore, doping Fe element is to copper
The electric property of zinc-tin-sulfur film has greatly improved effect.
Wherein, as shown in Figure 11, the photoelectric conversion efficiency η of the copper-zinc-tin-sulfur thin battery obtained when doping Fe content is 0.2
For 2.4%, open-circuit voltage Voc be 520mV, short circuit current Jsc is 10.22mAcm-2, fill factor FF be 45.2%.Explanation
Fe doping copper-zinc-tin-sulfur film is suitable for preparing thin-film solar cells.
Copper-zinc-tin-sulfur film, preparation method and solar battery provided by the invention, 1) it is mixed in copper-zinc-tin-sulfur film
Miscellaneous to have a small amount of Fe element, the doping of a small amount of Fe element can preferably promote the surface topography and photo electric of copper-zinc-tin-sulfur film
Can, it obtains bigger crystal grain while there is no miscellaneous phase generation.2) the copper-zinc-tin-sulfur film assembling doped with a small amount of Fe element is utilized
Solar battery photoelectric conversion efficiency with higher.3) using the method optimizing copper-zinc-tin-sulfur film of vulcanization annealing, can press down
The chemical balance for making above-mentioned chemical breakdown reaction moves right, and the loss of Sn and S element in copper-zinc-tin-sulfur film is reduced, to protect
Demonstrate,prove the crystalline quality of the copper-zinc-tin-sulfur film of production.
The above is only better embodiment of the invention, not the limitation to the present invention in any form, though
The right present invention has been that better embodiment is disclosed above, is not intended to limit the invention, any person skilled in the art,
Without departing from the scope of the present invention, when the technology contents using the disclosure above are modified or are modified to
With the equivalent implementations of variation, but without departing from the technical solutions of the present invention, according to the technical essence of the invention to
Any simple modification, equivalent change and modification that upper embodiment is done, all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. a kind of copper-zinc-tin-sulfur film of modification, which is characterized in that doped with Fe element in the copper-zinc-tin-sulfur film of the modification,
In the copper-zinc-tin-sulfur film of the modification, the ratio of the quality sum of the quality and zinc-iron element of ferro element is 0-1.
2. the copper-zinc-tin-sulfur film being modified as described in claim 1, which is characterized in that in the copper-zinc-tin-sulfur film of the modification
In the ratio of each component is: the ratio of the quality sum of the quality and zinc-tin element of copper be 0.9-1, the quality of Zn-ef ficiency with
The mass values of tin element are 0.9-1.3, and the ratio of the quality sum of the quality and copper zinc-tin element of element sulphur is 2-2.1.
3. a kind of preparation method of the copper-zinc-tin-sulfur film of modification, comprising steps of
Configure modified copper-zinc-tin-sulfur precursor solution: the proportion of each component in the copper-zinc-tin-sulfur precursor solution of the modification
Are as follows: the ratio of the quality sum of the quality and zinc-tin element of copper is 0.9-1, the quality of Zn-ef ficiency and the mass ratio of tin element
Value is 0.9-1.3, and the ratio of the quality sum of the quality and copper zinc-tin element of element sulphur is 2-2.1, the quality and zinc of ferro element
The ratio of the quality sum of ferro element is 0-1；
On the base layer by the copper-zinc-tin-sulfur precursor solution spin coating of the modification；
The pre-heat treatment is carried out to the copper-zinc-tin-sulfur precursor solution for the modification being spin-coated on the basal layer, obtains modification
Copper-zinc-tin-sulfur membrane sample；And
Vulcanization annealing is carried out to the copper-zinc-tin-sulfur film sample of the modification, to obtain the copper-zinc-tin-sulfur film of the modification.
4. the preparation method for the copper-zinc-tin-sulfur film being modified as claimed in claim 3, which is characterized in that the pre-heat treatment
Temperature is 300 degrees Celsius, and preheating time is 2 minutes.
5. the preparation method for the copper-zinc-tin-sulfur film being modified as claimed in claim 3, which is characterized in that the spin coating includes first
Low speed spin coating is carried out, rear to carry out high speed spin coating, the speed of low speed spin coating is 800 revs/min, and the speed of high speed spin coating is spin coating speed
3000 revs/min of degree.
6. the preparation method for the copper-zinc-tin-sulfur film being modified as claimed in claim 5, which is characterized in that the low speed spin coating
Time is 6 seconds, and the time of the high speed spin coating is 24 seconds.
7. the preparation method for the copper-zinc-tin-sulfur film being modified as claimed in claim 3, which is characterized in that carrying out vulcanization annealing
The step of before, the pre-heat treatment and the spin coating are alternately.
8. the preparation method for the copper-zinc-tin-sulfur film being modified as claimed in claim 3, which is characterized in that the vulcanization annealing packet
Include step:
Sulphur powder and the copper-zinc-tin-sulfur film sample of the modification are respectively placed in the same tube furnace；And
It anneals under vacuum and argon atmosphere.
9. the preparation method for the copper-zinc-tin-sulfur film being modified as claimed in claim 8, which is characterized in that the technique of the annealing
Parameter are as follows: annealing temperature is 580 DEG C, and annealing soaking time is 1 hour, and annealing partial pressure is 0.15bar.
10. a kind of solar battery, the solar battery includes a basal layer, a back electrode being formed on the substrate
The copper-zinc-tin-sulfur film that layer, the copper-zinc-tin-sulfur film of a modification being formed on the back electrode layer, one are formed in the modification
On buffer layer, one be formed on the buffer layer intrinsic zinc oxide Window layer, be formed in the intrinsic zinc oxide Window layer
On tin indium oxide Window layer and the top electrode that is formed in the tin indium oxide Window layer, which is characterized in that the modification
Copper-zinc-tin-sulfur film is prepared by the preparation method of the copper-zinc-tin-sulfur film of the described in any item modifications of claim 3-9.
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