CN101546791B

CN101546791B - Method for preparing CuInS2 ultrathin membrane and prepared CuInS2 ultrathin membrane

Info

Publication number: CN101546791B
Application number: CN2009100502670A
Authority: CN
Inventors: 穆帅; 康诗钊
Original assignee: East China University of Science and Technology
Current assignee: East China University of Science and Technology
Priority date: 2009-04-29
Filing date: 2009-04-29
Publication date: 2011-07-27
Anticipated expiration: 2029-04-29
Also published as: CN101546791A

Abstract

The invention provides a method for preparing a CuInS2 ultrathin membrane and the CuInS2 ultrathin membrane. The method comprises: A) modifying 3-sulfhydryl propyl trimethoxy silane on the surface of a substrate; B) immersing the modified substrate into an ethanol solution containing Cu<2+>, an ethanol solution containing In<3+> and an ethanol solution containing dithiol in turn; C) repeating the step B) for a plurality of times, and preparing a (-Cu<2+>-dithiol-In<3+>-dithiol-)n multilayered membrane; and D) roasting the (-Cu<2+>-dithiol-In<3+>-dithiol-)n multilayered membrane and cooling the (-Cu<2+>-dithiol-In<3+>-dithiol-)n multilayered membrane to the room temperature. The CuInS2 membrane provided by the invention is prepared by the method. By utilization of the method to prepare the CuInS2 ultrathin membrane, not only the reaction condition is mild and the equipment is simple but also the obtained CuInS2 nano ultrathin membrane has high crystallinity and is uniform and dense. Moreover, the method can control the layer number of the membrane by controlling the frequency of alternated immersion so as to control the thickness of the membrane as required.

Description

A kind of CuInS＜sub〉2＜/sub〉preparation method of ultrathin membrane and the CuInS＜sub of preparation〉2＜/sub〉ultrathin membrane

Technical field

The invention belongs to solar energy light absorption material field, specifically, relate to a kind of CuInS ₂The preparation method of ultrathin membrane and the CuInS of preparation ₂Ultrathin membrane.

Background technology

Using in the solar utilization technique at present the most directly is that electric energy is used with conversion of solar energy, therefore needs to make the solar-electrical energy conversion equipment.The main raw material(s) of making the solar-electrical energy conversion equipment is monocrystalline silicon and the vacuum condition thin-film material of preparation down, but above-mentioned material costs an arm and a leg, and has limited the large-scale application of solar energy.Therefore developing a kind of cheap photoelectric conversion material is the key of utilizing solar energy on a large scale.

And semi-conducting material CuInS ₂, having energy gap and solar spectrum is complementary, the optical absorption coefficient height also has very high theoretical light photoelectric transformation efficiency simultaneously, therefore, CuInS ₂Having important use and be worth aspect opto-electronic conversion, is a kind of light absorbent of very potential thin-film solar cells.

By to CuInS ₂Discovering of film, CuInS ₂The technology of preparing of film is very big to the influences such as composition, structure and photoelectric properties of film, and then influences the performance of thin-film solar cells.

Be the CuInS that obtains to be suitable for using ₂Film, people have carried out a large amount of research, and have set up many CuInS ₂The preparation method of film, for example chemical vapour deposition technique (CVD), sheath gas-phase reaction method, electrodeposition process, spray pyrolysis, metal organic chemical compound vapor deposition method (MOCVD), chemical bath deposition (CBD) etc., but said method generally all needs harsh preparation condition, as high vacuum and/or expensive instrument and equipment, thereby seriously influenced CuInS ₂The industrial applications of film.

In order to overcome above-mentioned defective, worked out the method for the film that under temperate condition, prepares, as absorption of continuous ionic layer and reaction (SILAR).But, adopt the SILAR legal system to be equipped with CuInS ₂During film, its key step is that substrate is being contained copper ion and In ³⁺Mixed solution alternately soaks with containing in the solution of sulphion, utilizes the sheath absorption on substrate surface to obtain CuInS with reaction then ₂Film.This method preparation condition gentleness, equipment needed thereby are simple, but resulting thin film crystallization is relatively poor, still can not satisfy industrial application requirements.

Therefore, set up a high-quality CuInS of preparation under temperate condition ₂The method of film is for CuInS ₂Make Application for Field at solar cell and have crucial meaning.

Summary of the invention

The objective of the invention is to, a kind of CuInS is provided ₂The preparation method of ultrathin membrane is with the high-quality CuInS of preparation under temperate condition ₂Ultrathin membrane.

A further object of the invention is, a kind of CuInS is provided ₂Ultrathin membrane.

Preparation method provided by the invention may further comprise the steps:

A) the 3-sulfydryl propyl trimethoxy silicane of substrate surface is modified;

B) with steps A) in substrate after the modification that obtains be immersed in successively and contain Cu ²⁺, dithiol, In ³⁺With soak in the ethanolic solution of dithiol;

C) repeating step B) repeatedly, with preparation (Cu ²⁺-dithiol-In ³⁺-dithiol-) _nMultilayer film;

D) with step C) in (Cu for preparing ²⁺-dithiol-In ³⁺-dithiol-) _nThe multilayer film roasting also naturally cools to room temperature, obtains CuInS ₂Ultrathin membrane.

CuInS provided by the invention ₂Ultrathin membrane is for adopting the CuInS of method for preparing ₂Ultrathin membrane.

Use method provided by the invention to prepare CuInS ₂Ultrathin membrane, reaction condition gentleness not only, equipment is simple, and the CuInS that obtains ₂Nano ultrathin membrane crystallization degree height, even compact; In addition, the number of plies that method of the present invention can be come controlling diaphragm by the number of times that control is alternately soaked, thereby the thickness of controlling diaphragm as required.

Description of drawings

Fig. 1 is preparation CuInS ₂The immersion process schematic diagram of ultrathin membrane.

Fig. 2 is the CuInS that embodiment 1～5 prepares ₂The x-ray diffraction pattern of ultrathin membrane.

Fig. 3 is the CuInS that method of the present invention obtains ₂The sem photograph of ultrathin membrane, wherein, Fig. 3 a is CuInS ₂The electron-microscope scanning figure on the surface of ultrathin membrane, Fig. 3 b are CuInS ₂The electron-microscope scanning figure in the cross section of ultrathin membrane.

Embodiment

Below in conjunction with specific embodiment, the invention will be further described.Should be understood that following examples only are used to the present invention is described but not are used to limit scope of the present invention.

The inventor is to CuInS ₂Find when the preparation of ultrathin membrane is studied, will be immersed in successively through the substrate (glass, quartz or monocrystalline silicon substrate) that MPS modifies and contain Cu ²⁺, dithiol, In ³⁺With in the ethanolic solution of dithiol (wherein, wherein, Cu ²⁺Be the chloride of copper, sulfate, nitrate, acetate etc., In ³⁺Be inidum chloride, indium sulfate, indium nitrate, indium acetate, dithiol is ethanthiol or dimercaptopropane), and repeatedly repeat above-mentioned soaking step, to prepare (Cu ²⁺-dithiol-In ³⁺-dithiol-) _nMultilayer film can obtain corresponding C uInS through roasting then ₂Ultrathin membrane, detailed process as shown in the Examples, wherein, immersion process is as shown in Figure 1.

Embodiment 1～5, CuInS ₂The ultrathin membrane preparation

1, substrate preliminary treatment

Place 50～120 ℃ chromic acid lotion to soak 15～45min substrate, so that substrate is cleaned up, use distilled water drip washing for several times then, dry then to remove chromic acid lotion fully, concrete treatment conditions are as shown in table 1.

Table 1, type of substrate and pretreatment condition

Embodiment	1	2	3	4	5
						Type of substrate	Glass	Quartzy	Glass	Monocrystalline silicon	Glass
The washing lotion temperature (℃)	50	80	80	100	120
						Soak time (min)	45	30	30	25	15

2, substrate surface 3-sulfydryl propyl trimethoxy silicane (MPS) is modified

Will be through the pretreated substrate of chromic acid lotion, under 90～150 ℃, (5mmolL in the toluene solution of MPS ^-1) refluxed 1～6 hour, use toluene and ethanol drip washing for several times then respectively, use N again ₂The substrate that air-flow will clean dries up, and promptly obtains the substrate of finishing MPS, and the condition of specifically modifying is as shown in table 2.

Table 2, substrate surface MPS modify condition

Embodiment	1	2	3	4	5
						Reflux temperature (℃)	90	130	110	110	150
Return time (hour)	6	2	3	4	1

3, (Cu ²⁺-dithiol-In ³⁺-dithiol-) _nThe multilayer film preparation

The substrate that MPS is modified is immersed in Cu successively ²⁺, dithiol, In ³⁺, and the ethanolic solution of dithiol in, soak time 30s～5min.After each substrate takes out from soak, all earlier substrate drip washing is clean with ethanol, use N again ₂It is dried up.

Repeat above step n time, prepare (the Cu of n layer ²⁺-dithiol-In ³⁺-dithiol-) _nMultilayer film, concrete preparation condition is shown in table 3 and table 4.

Table 3, Cu ²⁺, In ³⁺And dithiol

Embodiment	1	2	3	4	5
						Cu ²⁺	Copper chloride	Copper sulphate	Schweinfurt green	Copper nitrate	Copper sulphate
In ³⁺	Inidum chloride	Indium sulfate	Indium nitrate	Indium acetate	Indium nitrate
						Dithiol	Ethanthiol	Dimercaptopropane	Dimercaptopropane	Ethanthiol	Ethanthiol

Table 4, substrate surface MPS modify condition

4, CuInS ₂The ultrathin membrane preparation

Then, (the Cu that step 1～3 are prepared ²⁺-dithiol-In ³⁺-dithiol-) _nMultilayer film places tube furnace, at N ₂Under the atmosphere, after 1～8 hour, naturally cool to room temperature, promptly obtain CuInS in 230～450 ℃ of roastings ₂Ultrathin membrane, concrete preparation condition is as shown in table 5.

Table 5, CuInS ₂The ultrathin membrane preparation condition

Embodiment	1	2	3	4	5
						Sintering temperature (℃)	250	230	350	280	450
Roasting time (hour)	5	8	2	5	1

Embodiment 6, CuInS ₂The Performance Detection of ultrathin membrane

With the CuInS that obtains among the embodiment 1～5 ₂Ultrathin membrane carries out X-ray diffraction and detects, and diffracting spectrum as shown in Figure 2.

By the X-ray diffracting spectrum of Fig. 2 as seen, the CuInS of acquisition ₂Sharp-pointed diffraction maximum all appears in ultrathin membrane, shows the CuInS that obtains ₂Ultrathin membrane has good degree of crystallinity.

CuInS to obtaining simultaneously ₂Ultrathin membrane carries out electron-microscope scanning, and the electron-microscope scanning result as shown in Figure 3.

According to the result of Fig. 3, the CuInS of acquisition ₂Ultrathin membrane is very fine and close not to have hole, smooth surface, cover on the substrate equably, and THICKNESS CONTROL shows and utilizes this technology can prepare densification, CuInS uniformly about 200nm ₂Ultrathin membrane.

According to The above results, use method of the present invention to prepare CuInS ₂Ultrathin membrane, reaction condition gentleness not only, equipment is simple, and the CuInS that obtains ₂Nano ultrathin membrane crystallization degree height, even compact; In addition, the number of plies that method of the present invention can be come controlling diaphragm by the number of times that control is alternately soaked, thereby the thickness of controlling diaphragm as required.

Claims

1. CuInS ₂The preparation method of ultrathin membrane is characterized in that, said method comprising the steps of:

A) the 3-sulfydryl propyl trimethoxy silicane of substrate surface is modified;

B) substrate after will modifying is immersed in successively and contains Cu ²⁺, dithiol, In ³⁺With soak in the ethanolic solution of dithiol;

C) repeating step B) repeatedly, obtain (Cu ²⁺-dithiol-In ³⁺-dithiol-) _nMultilayer film;

D) (the Cu that will obtain ²⁺-dithiol-In ³⁺-dithiol-) _nThe multilayer film roasting also naturally cools to room temperature, obtains CuInS ₂Ultrathin membrane.

2. the method for claim 1 is characterized in that, described substrate is glass, quartz or monocrystalline silicon substrate.

3. the method for claim 1 is characterized in that, described 3-sulfydryl propyl trimethoxy silicane is modified in the toluene solution that contains 3-sulfydryl propyl trimethoxy silicane and refluxes.

4. method as claimed in claim 3 is characterized in that, described backflow is to reflux 1～6 hour in 90～150 ℃.

5. the method for claim 1 is characterized in that, the described Cu that contains ²⁺Ethanolic solution be the ethanolic solution that contains copper chloride, copper sulphate, copper nitrate or Schweinfurt green, described Cu ²⁺Concentration is 0.01～0.1mol/L.

6. the method for claim 1 is characterized in that, the described In that contains ³⁺Ethanolic solution be the ethanolic solution that contains inidum chloride, indium sulfate, indium nitrate or indium acetate, described In ³⁺Ethanolic solution in In ³⁺Concentration is 0.01～0.1mol/L.

7. the method for claim 1 is characterized in that, described dithiol is ethanthiol or dimercaptopropane, and described dithiol concentration is 0.01～0.5mol/L.

8. the method for claim 1 is characterized in that, described step B) in soak time be 30s～5min.

9. the method for claim 1 is characterized in that, described roasting is in 230～450 ℃ of roastings 1～8 hour.

10. as each described method in the claim 1～9, it is characterized in that, also comprise the pretreated step of substrate before the described steps A.

11. method as claimed in claim 10 is characterized in that, described substrate pre-treatment step is to place 50～120 ℃ chromic acid lotion to soak 15～45min substrate.

12. CuInS as each described method preparation in the claim 1～11 ₂Ultrathin membrane.