CN109904256A - A kind of copper-zinc-tin-sulfur film preparation method - Google Patents
A kind of copper-zinc-tin-sulfur film preparation method Download PDFInfo
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- CN109904256A CN109904256A CN201910018440.2A CN201910018440A CN109904256A CN 109904256 A CN109904256 A CN 109904256A CN 201910018440 A CN201910018440 A CN 201910018440A CN 109904256 A CN109904256 A CN 109904256A
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Abstract
The invention discloses a kind of copper-zinc-tin-sulfur film preparation method, the molybdenum electrode of 1 μ m-thick step: is plated on the clean surface SLG；It sputters to obtain copper-zinc-tin-sulfur film preformed layer with quaternary compound copper-zinc-tin-sulfur target；By the preformed layer prepared under above-mentioned condition in 570 ~ 590 DEG C without sulphur source in-situ annealing 25-35min.Formation mechenism of this method based on CZTS only needs a Cu-Zn-Sn-S target sputtering preformed layer and can obtain CZTS film by subsequent no sulphur source in-situ annealing, this method is the film build method being most simple and efficient at present, single target is prepared after preformed layer without sulphur source in-situ annealing, large-scale production suitable for copper-zinc-tin-sulfur film, and entire film forming procedure is completed in a vacuum chamber, pollution of the introduced contaminants to film can effectively be avoided, the sulphur content pressure for solving extraneous sulphur source, which is unable to accurately control, causes film to have the phenomenon that broken grain grain and large area cavity generate, the uniformity and single phase property of CZTS film greatly improved.
Description
Technical field
The present invention relates to a kind of copper-zinc-tin-sulfur film preparation methods, belong to new energy field.
Background technique
Novel quaternary compound semiconductor copper-zinc-tin-sulfur (2 ZnSnS 4 of Cu, abridge CZTS) is the widest with current application
The absorbed layer material copper indium gallium selenide (Cu (In, Ga) Se 2, abridge CIGS) of general unijunction hull cell belongs to chalcopyrite knot
Structure, difference are CZTS with the gallium (Ga) and indium (In) in tin (Sn) and zinc (Zn) substitution CIGS, with sulphur (S) substitution selenium (Se)
It constitutes, and your dilute element and toxic element is not contained again.Compared with CIGS, the band gap (1.5eV) of CZTS has and solar spectrum
It more preferably matches, and CZTS has the outstanding absorption coefficient of light same as CIGS (being greater than 10 4 cm -1), theoretical efficiency can
Up to 32.2%, due to containing a large amount of dilute your element (Ga, In) and toxic element (Se) in CIGS, so CZTS is generally considered
It is one of the optimal material for substituting CIGS.
It is well known that preparation CZTS film when, vulcanization annealing steps it is most important, but at this stage no matter which kind of annealing way
Additional sulphur source is required, sulphur content pressure is difficult accurately to control during this, and additional sulphur source is often because of the dirt of excessive element sulphur
Dye can not carry out more efficient in-situ annealing.This makes CZTS made from additional sulphur source small grains easily occur and connect in back
Touching region, there are a large amount of holes, and are easy to introduce other impurities generation complex centre during antivacuum.
Based on this consideration, researcher in this field wishes by simplifying technology difficulty, reducing preparation cost, raising technique
Reproducibility prepares good CZTS film.According to the Forming Mechanism of CZTS, special quaternary compound copper zinc-tin is directlyed adopt
Sulphur target sputtering preparation CZTS preformed layer can be in vulcanization annealing process as long as subsequent vulcanization annealing temperature does not exceed 600 DEG C
In effectively reduce and prevent the generation of Cu2-xS, Sn2-xS because there's almost no in preformed layer Cu and Sn simple substance and
Secondly Cu2-xS, Sn2-xS binary sulfide find that Cu's and Zn contains in the film obtained when sputtering CZTS target according to experiment
Amount is relatively on the low side, so it is poor copper that next, which requires finally obtained CZTS film, by the special component for copper-rich zinc-rich of CZTS target
The custerite structure of zinc-rich (Cu/ (Zn+Sn)=0.75 ~ 0.90, Zn/Sn=1.05 ~ 1.15), so the Zn in target contains
Amount causes Zn content in preformed layer to reduce also with respect to Sn higher because Zn can be easily separated in sputtering process.
Summary of the invention
In view of drawbacks described above of the existing technology, the object of the present invention is to provide a kind of simple processs, and reliable, component can
The good and copper-zinc-tin-sulfur film preparation method suitable for large-scale production of control, reproducibility.
Realizing the technical solution of the object of the invention is: a kind of copper-zinc-tin-sulfur film preparation method, real according to the following steps
It applies:
(1) substrate cleans: soda-lime glass successively being used cleanser, acetone, alcohol, deionized water are cleaned by ultrasonic, then in weight chromium
20 ~ 30min is impregnated in sour potassium solution, after be cleaned by ultrasonic again with deionized water, and with being dried with nitrogen；
(2) sputtering prepares the Mo back electrode of double-layer structure；
(3) by radio-frequency sputtering, using copper-zinc-tin-sulfur quaternary compound as target, deposition obtains the CZTS preformed layer of 900nm；
(4) it is passed through high pure nitrogen (99.99%) to sputtering chamber, the CZTS preformed layer sputtered in step 3 is carried out without sulphur source original position
Annealing, and CZTS film is obtained after natural cooling.
Further, in step (1), the potassium bichromate solution is 80 ~ 90 DEG C of supersaturated potassium bichromate solution.
Further, in step (2), the Mo back electrode of double-layer structure is successively in the operating air pressure of 1.5Pa, 0.3Pa, substrate
D.c. sputtering obtains under conditions of 160 DEG C of temperature, and wherein operating air pressure 1.5Pa sputtering time is 15min, operating air pressure 0.3Pa
Sputtering time is 50min.
Further, in step (3), the atomic ratio of Cu:Zn:Sn:S is 4.6:2.3:1 in copper-zinc-tin-sulfur quaternary compound:
16；Sputtering power is RF power supply 80W, and chamber pressure is 0.3Pa when sputtering.
Further, in step (4), no sulphur source in-situ annealing processing when temperature in 45 minutes from room temperature linear change to
570 ~ 590 DEG C and 25 ~ 35min is kept the temperature, rear cooled to room temperature obtains CZTS film.
Further, in step (4), at room temperature in sputtering chamber the air pressure of high pure nitrogen within the scope of 800-1100Pa.
Compared with prior art, the present invention has the advantage that (1) present invention is splashed using copper-zinc-tin-sulfur quaternary compound target
It penetrates, and the CZTS preformed layer is carried out without the processing of sulphur source in-situ annealing, it is (including solid without any additional sulphur source before and after annealing process
Body and gas sulphur source), entire film forming procedure is completed in a vacuum chamber, and dirt of the introduced contaminants to film can be effectively avoided
Dye.(2) the sulphur content pressure that the present invention solves extraneous sulphur source, which is unable to accurately control, causes film to have broken grain grain and large area cavity raw
At the phenomenon that, the uniformity and single phase property of CZTS film greatly improved.
Detailed description of the invention
Attached drawing is not intended to drawn to scale.In the accompanying drawings, identical or nearly identical group each of is shown in each figure
It can be indicated by the same numeral at part.For clarity, in each figure, not each component part is labeled.
Now, example will be passed through and the embodiments of various aspects of the invention is described in reference to the drawings, in which:
Fig. 1 is the scanning electron microscope diagram of the CZTS film surface of embodiment 1-3 preparation.
Fig. 2 is the XRD spectrum of the CZTS film of embodiment 1-3 preparation.
Fig. 3 is the Raman map of the CZTS film of embodiment 1-3 preparation.
Specific embodiment
In order to make the contents such as sedimentary sequence of the invention be easier to be understood, below according to specific embodiment and combine
Attached drawing, the present invention is described in further detail.
Various aspects with reference to the accompanying drawings to describe the present invention in the present invention, shown in the drawings of the embodiment of many explanations.
It is not intended to cover all aspects of the invention for embodiment disclosed by the invention.It should be appreciated that a variety of designs presented hereinbefore
And embodiment, and those of describe in more detail below design and embodiment can in many ways in any one come
Implement, this is to should be conception and embodiment disclosed in this invention to be not limited to any embodiment.In addition, disclosed by the invention
Some aspects can be used alone, or otherwise any appropriately combined use with disclosed by the invention.
The principle of the invention is: according to the Forming Mechanism of CZTS, directlying adopt special quaternary compound copper-zinc-tin-sulfur target and splashes
Preparation CZTS preformed layer is penetrated, it, can be in vulcanization annealing process effectively as long as subsequent vulcanization annealing temperature does not exceed 600 DEG C
Reduce and prevent the generation of Cu2-xS, Sn2-xS because there's almost no in preformed layer Cu and Sn simple substance and Cu2-xS,
Sn2-xS binary sulfide.And entire film forming procedure is completed in a vacuum chamber, and effectively introduced contaminants can be avoided to thin
The pollution of film.Being unable to accurately control this method solve the sulphur content pressure of extraneous sulphur source causes film to have broken grain grain and large area cavity
The uniformity and single phase property of CZTS film greatly improved in the phenomenon that generation.
Embodiment 1
(1) substrate cleans: soda-lime glass successively being used cleanser, acetone, alcohol, deionized water are cleaned by ultrasonic, then in weight chromium
Impregnate 30min in sour potassium solution, after be cleaned by ultrasonic again with deionized water, and with being dried with nitrogen；
(2) cleaned soda-lime glass is put into sputtering chamber, base vacuum is evacuated to 5.0 × 10 -4Pa, power 150W,
Sputtering pressure is respectively 1.5Pa (15min), 0.3Pa (50min), obtains 1 μm of molybdenum back on soda-lime glass by above-mentioned requirements
Electrode film.
(3) preparation of copper-zinc-tin-sulfur film preformed layer: using the monocycle layering sputtering CuS(Cu:S=1:1), ZnS(Zn:S=
1:1) and SnS(Sn:S=1:1) target, base vacuum is same as above, in sputtering power 90W, 100 DEG C of underlayer temperature, operating air pressure 0.5Pa,
Sputtering 40min, 72min and 60min respectively is sputtered under conditions of sample stage revolving speed 8rpm, obtains the CZTS of overall thickness about 900nm
Preformed layer.
(4) preparation of copper-zinc-tin-sulfur film absorbed layer: the CZTS preformed layer that upper step obtains is together with the sublimed sulfur of 50mg
It is put into semi-enclosed graphite boat, then graphite boat is pushed into the quartz ampoule of high temperature vulcanized furnace at 570 ~ 590 DEG C, normal pressure, nitrogen
The lower vulcanization annealing 25min of protection.Cooled to room temperature obtains CZTS film, and scanning electron microscope diagram is shown in Fig. 1.
Embodiment result: in conjunction with table 1 and Fig. 1-Fig. 3, the elemental constituent of CZTS film prepared by embodiment 1 meets maintenance
The stable ratio of CZTS chemical potential, but still contain secondary phase.Crystal structure degree is preferable, but has the more hole for decomposing and generating.
And MoS2The content detected is still more.These results will directly affect the last incident photon-to-electron conversion efficiency of CZTS solar cell.
Embodiment 2
(1) substrate cleans: soda-lime glass successively being used cleanser, acetone, alcohol, deionized water are cleaned by ultrasonic, then in weight chromium
Impregnate 30min in sour potassium solution, after be cleaned by ultrasonic again with deionized water, and with being dried with nitrogen；
(2) cleaned soda-lime glass is put into sputtering chamber, base vacuum is evacuated to 5.0 × 10-4 Pa, power 150W,
Sputtering pressure is respectively 1.5Pa (15min), 0.3Pa (50min), obtains 1 μm of molybdenum back on soda-lime glass by above-mentioned requirements
Electrode film.
(3) preparation of copper-zinc-tin-sulfur film preformed layer: the common quaternary compound copper-zinc-tin-sulfur target of use be (Cu:Zn:Sn:S's
Atomic ratio is 2:1:1:4) sputtering, base vacuum is same as above, in sputtering power 90W, 100 DEG C of underlayer temperature, operating air pressure 0.5Pa,
130min is sputtered under conditions of sample stage revolving speed 8rpm, obtains the CZTS preformed layer of about 900nm.
(4) high pure nitrogen, room temperature bottom chamber High Purity Nitrogen the preparation of copper-zinc-tin-sulfur film absorbed layer: are passed through to sputtering chamber
Gas air pressure is 1000Pa, by CZTS preformed layer without sulphur source in-situ annealing, temperature in 45 minutes from room temperature linear change to 570 ~
590 DEG C and 30min is kept the temperature, rear cooled to room temperature, scanning electron microscope diagram is shown in Fig. 1.
Embodiment result: in conjunction with table 1 and Fig. 1-Fig. 3, the elemental constituent of CZTS film prepared by embodiment 2 does not meet maintenance
The stable ratio of CZTS chemical potential, and it is out of proportion serious.Crystal structure degree is poor, has many secondary phases, fails to form single-phase
CZTS crystal.In the target for meeting chemical element metering ratio, since each element sputtering ratio is different, so causing to sputter
To target do not meet element metering ratio.These results will directly affect the last incident photon-to-electron conversion efficiency of CZTS solar cell.
Embodiment 3
(1) substrate cleans: soda-lime glass successively being used cleanser, acetone, alcohol, deionized water are cleaned by ultrasonic, then in weight chromium
Impregnate 30min in sour potassium solution, after be cleaned by ultrasonic again with deionized water, and with being dried with nitrogen；
(2) cleaned soda-lime glass is put into sputtering chamber, base vacuum is evacuated to 5.0 × 10-4 Pa, power 150W,
Sputtering pressure is respectively 1.5Pa (15min), 0.3Pa (50min), obtains 1 μm of molybdenum back on soda-lime glass by above-mentioned requirements
Electrode film.
(3) preparation of copper-zinc-tin-sulfur film preformed layer: the special quaternary compound copper-zinc-tin-sulfur target of use be (Cu:Zn:Sn:S's
Atomic ratio is 2.2:1.2:0.95:6) sputtering, base vacuum is same as above, in sputtering power 90W, 100 DEG C of underlayer temperature, operating air pressure
130min is sputtered under conditions of 0.5Pa, sample stage revolving speed 8rpm, obtains the CZTS preformed layer of about 900nm.
(4) high pure nitrogen, room temperature bottom chamber High Purity Nitrogen the preparation of copper-zinc-tin-sulfur film absorbed layer: are passed through to sputtering chamber
Gas air pressure is 1000Pa, by CZTS preformed layer without sulphur source in-situ annealing, temperature in 45 minutes from room temperature linear change to 570 ~
590 DEG C and 30min is kept the temperature, rear cooled to room temperature, scanning electron microscope diagram is shown in Fig. 1.
Embodiment result: in conjunction with table 1 and Fig. 1-Fig. 3, since target atom sputter rate is different, using of the invention special
The elemental constituent of CZTS film prepared by target, which meets, maintains the stable ratio of CZTS chemical potential, almost without secondary phase and
Crystal structure degree is preferably and almost without the content MoS detected2.The last incident photon-to-electron conversion efficiency of these CZTS solar cells has
Beneficial effect.
The EPMA composition analysis result of the copper-zinc-tin-sulfur film absorbed layer of 1 embodiment 1-3 of table preparation
| Embodiment | Cu/(Sn+Zn) | Zn/Sn | S/M |
| 1 | 0.82 | 1.17 | 1.02 |
| 2 | 0.48 | 0.53 | 0.61 |
| 3 | 0.81 | 1.12 | 0.98 |
Claims (9)
1. a kind of preparation method of copper-zinc-tin-sulfur film, which comprises the following steps:
(1) by radio-frequency sputtering, on the Mo back electrode of double-layer structure, using copper-zinc-tin-sulfur quaternary compound as target, deposition is obtained
Copper-zinc-tin-sulfur preformed layer；
(2) it is passed through high pure nitrogen to sputtering chamber, copper-zinc-tin-sulfur preformed layer is carried out without the processing of sulphur source in-situ annealing, natural cooling
After obtain copper-zinc-tin-sulfur film.
2. preparation method as described in claim 1, which is characterized in that the Mo back electrode of the double-layer structure is in soda-lime glass
Sputtering sedimentation obtains on substrate.
3. preparation method as described in claim 1, which is characterized in that the Mo back electrode of double-layer structure successively 1.5Pa,
The operating air pressure of 0.3Pa, d.c. sputtering obtains under conditions of 160 DEG C of soda-lime glass underlayer temperature, wherein operating air pressure 1.5Pa
Sputtering time is 15min, and operating air pressure 0.3Pa sputtering time is 50min.
4. preparation method as claimed in claim 2 or claim 3, which is characterized in that the soda-lime glass substrate is by by sodium calcium glass
Glass successively uses cleanser, acetone, alcohol, deionized water ultrasonic cleaning and then the supersaturated potassium bichromate solution at 80 ~ 90 DEG C
20 ~ 30min of middle immersion, after be cleaned by ultrasonic again with deionized water, and obtained with after being dried with nitrogen.
5. preparation method as described in claim 1, which is characterized in that the original of Cu:Zn:Sn:S in copper-zinc-tin-sulfur quaternary compound
Son is than being 4.6:2.3:1:16.
6. preparation method as described in claim 1, which is characterized in that when depositing copper-zinc-tin sulphur preformed layer, sputtering power RF
Power supply 80W, chamber pressure is 0.3Pa when sputtering.
7. preparation method as described in claim 1, which is characterized in that temperature is in 45 minutes when the processing of no sulphur source in-situ annealing
From room temperature linear change to 570 ~ 590 DEG C and 25 ~ 35min is kept the temperature, rear cooled to room temperature obtains copper-zinc-tin-sulfur film.
8. preparation method as described in claim 1, which is characterized in that it is passed through high pure nitrogen to sputtering chamber at room temperature, it is high-purity
Nitrogen pressure is within the scope of 800-1100Pa.
9. preparation method as described in claim 1, which is characterized in that copper-zinc-tin-sulfur preformed layer with a thickness of 900nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112736161A (en) * | 2020-12-30 | 2021-04-30 | 中山大学 | Copper-zinc-tin-sulfur-based film precursor with cyclic quantum well structure and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102709393A (en) * | 2012-06-06 | 2012-10-03 | 成都先锋材料有限公司 | Method for preparing thin-film solar cells from copper-zinc-tin sulfur compound single target materials |
| WO2013129468A1 (en) * | 2012-02-28 | 2013-09-06 | 国立大学法人大阪大学 | Method for forming czts semiconductor thin film, and photoelectric conversion element |
| KR20150064930A (en) * | 2013-12-04 | 2015-06-12 | 한국생산기술연구원 | Fabrication Method of Flexible CZTS Films and its application to Thin Film Solar Cells and Thin Film Solar Cells |
| CN105428212A (en) * | 2015-11-11 | 2016-03-23 | 云南师范大学 | Method for preparing copper-zinc-tin-selenide thin film absorber layer by single target sputtering |
| CN105826425A (en) * | 2015-12-24 | 2016-08-03 | 云南师范大学 | Preparation method for preparing copper-zinc-tin-sulfide (Cu-Zn-Sn-S) thin film solar cell |
-
2019
- 2019-01-09 CN CN201910018440.2A patent/CN109904256A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2013129468A1 (en) * | 2012-02-28 | 2013-09-06 | 国立大学法人大阪大学 | Method for forming czts semiconductor thin film, and photoelectric conversion element |
| CN102709393A (en) * | 2012-06-06 | 2012-10-03 | 成都先锋材料有限公司 | Method for preparing thin-film solar cells from copper-zinc-tin sulfur compound single target materials |
| KR20150064930A (en) * | 2013-12-04 | 2015-06-12 | 한국생산기술연구원 | Fabrication Method of Flexible CZTS Films and its application to Thin Film Solar Cells and Thin Film Solar Cells |
| CN105428212A (en) * | 2015-11-11 | 2016-03-23 | 云南师范大学 | Method for preparing copper-zinc-tin-selenide thin film absorber layer by single target sputtering |
| CN105826425A (en) * | 2015-12-24 | 2016-08-03 | 云南师范大学 | Preparation method for preparing copper-zinc-tin-sulfide (Cu-Zn-Sn-S) thin film solar cell |
Non-Patent Citations (1)
| Title |
|---|
| 赵其深等: "单靶溅射制备铜锌锡硫薄膜及原位退火研究", 《物理学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112736161A (en) * | 2020-12-30 | 2021-04-30 | 中山大学 | Copper-zinc-tin-sulfur-based film precursor with cyclic quantum well structure and preparation method thereof |
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Application publication date: 20190618 |