CN101805890A - Method for in-situ growth of Cu2ZnSnS4 photovoltaic thin film - Google Patents
Method for in-situ growth of Cu2ZnSnS4 photovoltaic thin film Download PDFInfo
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- CN101805890A CN101805890A CN200910226611A CN200910226611A CN101805890A CN 101805890 A CN101805890 A CN 101805890A CN 200910226611 A CN200910226611 A CN 200910226611A CN 200910226611 A CN200910226611 A CN 200910226611A CN 101805890 A CN101805890 A CN 101805890A
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Abstract
The invention relates to a method for the in-situ growth of a Cu2ZnSnS4 photovoltaic thin film, which is characterized by taking the mixed gas of hydrogen sulfide and argon as a sputtering gas, taking metal copper target, zinc target and tin target respectively as a Cu source, a Zn source and a Sn source, and carrying out the in-situ growth of the thin film in a reactive magnetic co-sputtering mode, wherein the pressure in a sputtering chamber during sputtering is 0.05Pa-10Pa, the distance between the target material and a substrate is 3 to 15cm, the sputtering power of each target is 15 to 300W, the substrate has the temperature of 20 to 700 DEG C and rotates at the rate of 0 to 100 rpm, the thickness of the grown thin film is 0.2 to 5 Mu m. The preparation method has simple process and lower cost, the prepared thin film has good component uniformity, high crystallization quality and superior optical and electrical properties.
Description
Technical field
The invention belongs to the photoelectric material technical field of new energies, relate to growth method as a kind of compound semiconductor film of thin film solar cell light absorption layer.
Background technology
The development solar cell is to solve the energy dilemma go from bad to worse and the effective way of environmental pollution.In all kinds of solar cells, CuIn
1-xGa
xSe
2(CIGS) thin film solar cell is considered to one of solar cell of most important and tool development prospect with its good photovoltaic property.Yet, CuIn
1-xGa
xSe
2In in the compound, Ga and Se are dissipated metals, cost an arm and a leg and reserves limited.Therefore, seek contain the high abundance element and cheaply the light absorbing zone thin-film material substitute CuIn
1-xGa
xSe
2Become the important topic of pendulum in face of us.It must be noted that in order to realize the large-scale practical application of solar cell, light absorption layer material is except requiring low cost, starting material have obtained, also should possess can and CuIn
1-xGa
xSe
2Comparable premium properties comprises: suitable (1.2～1.5eV) and adjustable band gap, bigger photoabsorption coefficient in the visible-range, high electronic mobility particularly has electricity tolerance etc. preferably to defective and crystal boundary.Research at present at most, to be considered to the most potential equivalent material be the Cu that substitutes 1 In atom with 0.5 Zn atom and 0.5 Sn atom
2ZnSnS
4(CZTS), reached 6.7% with its highest transformation efficiency of solar cell of making.
At present, Cu
2ZnSnS
4Film all is to adopt the technology based on thermal activation to prepare, and promptly realizes the reaction between each constituent element and forms required compound film by heat, mainly comprises evaporation and two kinds of technological lines of preformed layer postcure.Wherein the film quality of evaporation preparation is higher, and is poor but the development bottleneck of this technology maximum is a large-area uniformity, is difficult to obtain practical application.The preformed layer postcure is to adopt methods such as sputter, plating to prepare the alloy preformed layer earlier, and then preformed layer is heat-treated (sulfuration), obtains Cu
2ZnSnS
4Film, this method is easy to realize the large-area preparation of film, but has problems such as complex process, long flow path, circulation ratio be bad.Therefore, in order to realize the large-scale application of thin film solar cell, development one step preparation big area, high quality Cu
2ZnSnS
4The method of film is necessary.Reactive sputtering is well positioned to meet this requirement.
Summary of the invention
The purpose of this invention is to provide an a kind of step acquisition big area and high quality Cu that be easy to
2ZnSnS
4The in-situ growth technology of photovoltaic film.
Reactive sputtering reacts with quilt target atoms metal that sputter out, high energy, and form the target compound film on substrate by reactant gases is introduced in the sputter gas.This method and general thermal activation process have the difference of essence, it not only can realize one step of the low temperature growth in situ of film, and because the high energy target atoms metal that is sputtered out is just fully reacting chemical combination with reactant gases in the substrate operational process, so reactive sputtering can be regulated and control the thing phase composite and the microstructure of deposit film very easily, overcome traditional thermal activation technology and be subjected to reactive behavior, preformed layer quality and heating cycle etc. to influence the deficiency that produces two second phases and various defectives.In addition, this method also has technical process weak point, favorable reproducibility, the advantage that the traditional hot activating technologies such as large area deposition of suitable film can't possess.
To achieve these goals, technical scheme of the present invention is:
A kind of growth in situ Cu
2ZnSnS
4The photovoltaic film method, it is characterized in that: described preparation method with hydrogen sulfide and argon gas mixed gas as sputter gas, respectively as Cu source, Zn source and Sn source, carry out the growth in situ of film with metallic copper target, zinc target and tin target in the mode of magnetic control reaction cosputtering.
Sputter indoor gas total pressure is 0.05Pa～10Pa during sputter, the volume fraction of hydrogen sulfide is 1%～100% in the sputter gas, the distance of target and substrate is 3～15cm, underlayer temperature is 20～700 ℃, and with the rotation of 0～100 rpm speed, the sputtering power of each target is 15～300W.
Each target can carry out direct current or radio frequency magnetron reactive sputtering.
Obtain Cu
2ZnSnS
4The thickness of photovoltaic film is 0.2～5 μ m.
Preparation method of the present invention has realized Cu
2ZnSnS
4One step growth in situ of photovoltaic film, and compare with traditional method based on thermal activation, this method prepared film have good big area homogeneity of ingredients, pure thing phase composite and high crystalline quality, also possess superior optics, electrical properties simultaneously.In addition, compare traditional thermal activation base technology, this legal system is equipped with Cu
2ZnSnS
4Photovoltaic film also has simple, the advantages such as cost is lower, favorable reproducibility of technology.
Description of drawings
Fig. 1 is the Cu that the present invention obtains
2ZnSnS
4The typical shape appearance figure of film.
Fig. 2 is the Cu that the present invention obtains
2ZnSnS
4The exemplary x-ray diffractogram of film.
Fig. 3 is the Cu that the present invention obtains
2ZnSnS
4The typical light absorption spectrum of film.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but these embodiment must not be interpreted as limiting the scope of the invention.
Adopt Cu target, Zn target and Sn target respectively as Cu source, Zn source and Sn source, adopt the mode of d.c. sputtering, sputtering power is respectively 80W, 60W and 45W; Mixed gas with hydrogen sulfide and argon gas is a sputter gas, and the volume fraction of hydrogen sulfide is 10% in the mixed gas, and sputtering pressure is 0.08Pa, the distance of target and substrate is 10cm, underlayer temperature is 40 ℃, and rotates with 10 rpms speed, carries out growth in situ.Obtaining thickness is the Cu of 1 μ m
2ZnSnS
4Photovoltaic film, its conduction type are the p type, and band gap width is 1.50eV.
Embodiment 2
Adopt Cu target, Zn target and Sn target respectively as Cu source, Zn source and Sn source, adopt the mode of d.c. sputtering, sputtering power is respectively 60W, 40W and 35W; With hydrogen sulfide is sputter gas, and sputtering pressure is 1Pa, and the distance of target and substrate is 12cm, and underlayer temperature is 500 ℃, and rotates with 4 rpms speed, carries out growth in situ.Obtaining thickness is the Cu of 0.8 μ m
2ZnSnS
4Photovoltaic film, performance perameters such as its photoelectricity are as follows:
| Thickness (μ m) | Resistivity (Ω cm) | Hall coefficient (m 2/C) | Hall mobility (cm 2V -1s -1) | Carrier concentration (cm -3) | Conduction type | Photoabsorption coefficient (cm -1) | Energy gap (eV) |
| ??0.8 | ??5.4 | ??160.5 | ?29.75 | ??3.889×10 16 | ??p | ??1.24×10 4 | ??1.52 |
Embodiment 3
Adopt Cu target, Zn target and Sn target respectively as Cu source, Zn source and Sn source, adopt the mode of radio-frequency sputtering, sputtering power is respectively 75W, 45W and 40W; Mixed gas with hydrogen sulfide and argon gas is a sputter gas, and the volume fraction of hydrogen sulfide is 50% in the mixed gas, and sputtering pressure is 3Pa, and the distance of target and substrate is 11cm, and underlayer temperature is 450 ℃, does not rotate and carries out growth in situ.Obtaining thickness is the Cu of 2 μ m
2ZnSnS
4Photovoltaic film, its conduction type are the p type, and band gap width is 1.48eV.
Embodiment 4
Adopt Cu target, Zn target and Sn target respectively as Cu source, Zn source and Sn source, adopt the mode of radio-frequency sputtering, sputtering power is respectively 100W, 75W and 60W; Mixed gas with hydrogen sulfide and argon gas is a sputter gas, and the volume fraction of hydrogen sulfide is 80% in the mixed gas, and sputtering pressure is 8Pa, the distance of target and substrate is 11cm, underlayer temperature is 550 ℃, and rotates with 80 rpms speed, carries out growth in situ.Obtaining thickness is the Cu of 1.5 μ m
2ZnSnS
4Photovoltaic film, its conduction type are the p type, and band gap width is 1.47eV.
Claims (4)
1. growth in situ Cu
2ZnSnS
4The photovoltaic film method is characterized in that: as sputter gas, respectively as Cu source, Zn source and Sn source, carry out the growth in situ of film with metallic copper target, zinc target and tin target in the mode of magnetic control reaction cosputtering with hydrogen sulfide and argon gas mixed gas.
2. growth in situ Cu according to claim 1
2ZnSnS
4The photovoltaic film method, it is characterized in that: the interior gas pressure intensity of sputtering chamber is 0.05Pa～10Pa during sputter, the volume fraction of hydrogen sulfide is 1%～100% in the sputter gas, the distance of target and substrate is 3～15cm, underlayer temperature is 20～700 ℃, and with the rotation of 0～100 rpm speed, the sputtering power of each target is 15～300W.
3. growth in situ Cu according to claim 1 and 2
2ZnSnS
4The photovoltaic film method is characterized in that: each target carries out direct current or radio frequency magnetron reactive sputtering.
4. growth in situ Cu according to claim 1 and 2
2ZnSnS
4The photovoltaic film method is characterized in that: the thickness of described film is 0.2～5 μ m.
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| CN200910226611A CN101805890A (en) | 2009-12-14 | 2009-12-14 | Method for in-situ growth of Cu2ZnSnS4 photovoltaic thin film |
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887539A (en) * | 2012-09-24 | 2013-01-23 | 许昌学院 | Chemical method for performing in-situ preparation of nano sulfur-tin-zinc-copper quaternary compound photovoltaic film |
| CN103715282A (en) * | 2013-12-10 | 2014-04-09 | 西安石油大学 | Cu2ZnSnS4 thin-film solar cell, preparation method and photoelectric conversion system thereof |
| CN104157734A (en) * | 2014-08-11 | 2014-11-19 | 华东师范大学 | Method of preparing CuZnGe sulfide/ CuZnGe selenide film solar cell absorption layer |
| CN104370302A (en) * | 2014-10-23 | 2015-02-25 | 上海交通大学 | Nano-pouring synthetic method of copper-zinc-tin-sulfur nano-crystal |
| CN105821376A (en) * | 2015-12-24 | 2016-08-03 | 云南师范大学 | Preparation method for copper-zinc-tin sulfide target |
| CN110034271A (en) * | 2018-01-12 | 2019-07-19 | 中南大学 | A kind of CZTS film lithium cell cathode and its preparation and application |
| CN110280926A (en) * | 2019-06-25 | 2019-09-27 | 上海大学 | The high-throughput preparation method of Sn-Zn-Cu solder |
-
2009
- 2009-12-14 CN CN200910226611A patent/CN101805890A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887539A (en) * | 2012-09-24 | 2013-01-23 | 许昌学院 | Chemical method for performing in-situ preparation of nano sulfur-tin-zinc-copper quaternary compound photovoltaic film |
| CN102887539B (en) * | 2012-09-24 | 2014-10-29 | 许昌学院 | Chemical method for performing in-situ preparation of nano sulfur-tin-zinc-copper quaternary compound photovoltaic film |
| CN103715282A (en) * | 2013-12-10 | 2014-04-09 | 西安石油大学 | Cu2ZnSnS4 thin-film solar cell, preparation method and photoelectric conversion system thereof |
| CN103715282B (en) * | 2013-12-10 | 2015-06-17 | 西安石油大学 | Cu2ZnSnS4 thin-film solar cell, preparation method and photoelectric conversion system thereof |
| CN104157734A (en) * | 2014-08-11 | 2014-11-19 | 华东师范大学 | Method of preparing CuZnGe sulfide/ CuZnGe selenide film solar cell absorption layer |
| CN104157734B (en) * | 2014-08-11 | 2016-09-14 | 华东师范大学 | A kind of preparation method of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell |
| CN104370302A (en) * | 2014-10-23 | 2015-02-25 | 上海交通大学 | Nano-pouring synthetic method of copper-zinc-tin-sulfur nano-crystal |
| CN105821376A (en) * | 2015-12-24 | 2016-08-03 | 云南师范大学 | Preparation method for copper-zinc-tin sulfide target |
| CN110034271A (en) * | 2018-01-12 | 2019-07-19 | 中南大学 | A kind of CZTS film lithium cell cathode and its preparation and application |
| CN110280926A (en) * | 2019-06-25 | 2019-09-27 | 上海大学 | The high-throughput preparation method of Sn-Zn-Cu solder |
| CN110280926B (en) * | 2019-06-25 | 2021-11-09 | 上海大学 | High-flux preparation method of Sn-Zn-Cu solder |
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Open date: 20100818 |