CN102104086B

CN102104086B - Patterned composite film preparation method for reinforcing photo-absorption of titanium dioxide film

Info

Publication number: CN102104086B
Application number: CN2009101177455A
Authority: CN
Inventors: 贾均红; 卢永娟
Original assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Current assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Priority date: 2009-12-18
Filing date: 2009-12-18
Publication date: 2012-11-14
Anticipated expiration: 2029-12-18
Also published as: CN102104086A

Abstract

The invention discloses a patterned composite film preparation method for reinforcing photo-absorption of a titanium dioxide film. The method comprises the following steps: preparing a TiO2 nano-film on a glass substrate by using Ti(SO4)2 and H2O2 as precursor solutions; preparing a patterned self-assembled monomolecular film on the surface of the TiO2 nano-film by utilizing an ultraviolet photoetching technology; and selectively depositing Cu2S nano-crystal, and preparing the patterned Cu2S nano-film with complete pattern, clear boundary and compact structure on the surface of the TiO2 nano-film by utilizing a chemical bath method. The patterned Cu2S nano-film is used as a light absorption layer, and the TiO2 nano-film is used as an electron injecting layer to form p-n heterojunction of a patterned micro-structure Cu2S/TiO2 composite film, so the light absorption strength of the TiO2 nano-film can be effectively improved, the wavelength range of light absorption is enlarged, and the solar energy absorption efficiency of the film is further improved, thus the patterned composite film has wide application range in the fields of solar cells, photoswitches, photoelectric conversion, optical storage and the like.

Description

Strengthen the patterning preparation method of composite film of titanium deoxid film light absorption

Technical field

The present invention relates to the technology of preparing of semiconductor patterning film, particularly relate at titanium dioxide nano-film surface preparation patterning nanometer Cu ₂The S film is to strengthen the laminated film technology of preparing of sunlight absorption efficiency.

Background technology

Cu ₂S has good photoelectric properties as a kind of p-type, semiconductor material, the about 1.2eV of its energy gap.With Cu ₂S is the p-Cu of p-N-type semiconductor N ₂The electricity conversion of S/n-CdS heterojunction solar battery can reach on 10%, but owing to CdS poor stability, poisonous, reason such as interface charge carrier transfer rate is lower, has limited its further development and practical application.Titanium dioxide is a kind of typical n-type, semiconductor material; Owing to have unique photoelectricity physics, photocatalysis performance and excellent chemical stability; Has important application at aspects such as solar cell, optoelectronic switch and optical storages; It is the fastest to become development in recent years, has one of scientific research field of vigor most, also is the optimal selection that replaces n-CdS to prepare heterojunction solar battery.

Development with technology has great significance patterning techniques for modern science.It is reported the TiO of patterning ₂After film was processed solar cell, its photoelectric conversion efficiency was 10 times of non-patterned film, and this is because increasing of interface connection causes surface area to increase.Chen etc. find photoelectric current in experiment, the photocatalysis behavior strengthens along with reducing of pattern dimension, so Optical Electro-Chemistry character can be regulated and control through the pattern dimension size.Had many at present about p-Cu _xS/n-TiO ₂The report of laminated film, but about with Cu _xThe Cu that S modifies with patterning micro-structural _xS/TiO ₂The preparation of nano compound film in order to the patent of the sunlight absorption efficiency that improves film, does not also appear in the newspapers so far.

Summary of the invention

The object of the present invention is to provide the preparation method of the patterning nano compound film of simple, with low cost, the eco-friendly enhancing titanium deoxid film of a kind of technology absorbing properties.

The present invention is with Ti (SO ₄) ₂And H ₂O ₂For precursor solution prepares TiO on substrate of glass ₂Nano thin-film; The technology of utilizing ultraviolet photolithographic then is at TiO ₂The self-assembled monolayer of nano thin-film surface preparation patterning; Utilizing the method for chemical bath at last, is complexing agent with EDTA, CuSO ₄5H ₂O and Na ₂S ₂O ₃Be precursor solution, optionally deposit Cu ₂S is nanocrystalline, at TiO ₂Nano thin-film surface preparation pattern is complete, the patterning nanometer Cu of sharpness of border, compact structure ₂The S film.

A kind of patterning preparation method of composite film that strengthens the titanium deoxid film light absorption is characterized in that step is following:

1) TiO ₂The preparation of film: substrate of glass is immersed the absolute methanol solution of 3-aminopropyl triethoxysilane (APTS), assemble under the room temperature, clean with absolute methanol, secondary water successively after the taking-up, and dry up with nitrogen; Get Ti (SO then ₄) ₂, H ₂O ₂Form precursor solution with water, and adjusting pH value is about 1.6; The substrate of glass that then surface is had an APTS places this forerunner's liquid solution, 70～80 ℃ of deposition 20～60min;

2)-CH ₃/-NH ₂Constructing of-SAMs patterned surface: with the made TiO of step (1) ₂Nano thin-film places the hexane solution of octadecyl trichlorosilane (OTS), assembles under the room temperature, takes out the back and cleans with n-hexane, and dry up with nitrogen; The TiO that has OTS then on the surface ₂Place mask and ultraviolet lighting on the nano thin-film, in the process of illumination, the OTS SAMs of exposure area becomes hydroxyl, has obtained-OH/-CH ₃The surface of SAMs patterning; To have again-OH/-CH ₃The absolute methanol solution of 3-aminopropyl triethoxysilane (APTS) is put in the substrate of SAMs patterning, assembles under the room temperature, obtains-CH ₃/-NH ₂Constructing of-SAMs patterned surface;

3) Cu ₂The preparation of S patterned film: step (2) substrate of patterning SAMs is put into the precursor solution that contains copper sulphate, sodium thiosulfate, EDTA, and regulating the pH value is 1～3,65-75 ℃ of deposition twice, each 0.5～1h; At last to Cu ₂The S film is sintering processes under 200～300 ℃ of nitrogen protections, at TiO ₂The nano thin-film surface obtains that pattern is complete, the patterning nanometer Cu of sharpness of border, compact structure ₂The S film.

In the such scheme:

Cu with patterning ₂The S film is as the absorbed layer of light, TiO ₂Be electron injecting layer, this structure can effectively stop the compound of electronics and hole;

The nanometer Cu of preparation ₂S optionally is deposited under the inducing of monomolecular film-NH ₂The surface, and-CH ₃The surface does not almost deposit;

The composition of the patterned film of preparation is pure Cu ₂The S nano crystal.

Technical characterstic of the present invention is:

1) technology of the present invention is simple, with low cost, environmental friendliness, is easy to realize.

2) has active group (NH through chemisorbed in substrate surface formation ₂) monomolecular film, use monomolecular film and reduce inorganic one-tenth nuclear barrier, (70 ℃) are induced nucleation and growth at a lower temperature.

3) complete, the sharpness of border of the patterned film pattern of the present invention preparation, compact structure have good stable property and high selectivity.

4) the prepared patterned film of the present invention not only can effectively improve TiO ₂The optical absorption intensity of nano thin-film, and enlarged the light absorption wavelength scope, thus the efficiency of light absorption of further enhancement film.Have broad application prospects at aspects such as solar cell, optoelectronic switch, opto-electronic conversion and optical storages.

Embodiment

Embodiment 1:

1) TiO ₂The preparation of film: at first substrate of glass is immersed the absolute methanol solution of 5mM 3-aminopropyl triethoxysilane (APTS), assemble 3h under the room temperature, clean with absolute methanol, secondary water successively after the taking-up, and dry up with nitrogen; Get 0.06g Ti (SO then ₄) ₂, 0.058g H ₂O ₂Form precursor solution with water, and adjusting pH value is about 1.6; The substrate of glass that then surface is had an APTS places this forerunner's liquid solution, 80 ℃ of deposition 20min.

2)-CH ₃/-NH ₂Constructing of-SAMs patterned surface: at first with the made TiO of step (1) ₂Nano thin-film places the hexane solution of 5mM octadecyl trichlorosilane (OTS), assembles 1h under the room temperature, takes out the back and cleans with n-hexane, and dry up with nitrogen.The TiO that has OTS then on the surface ₂Place mask and ultraviolet lighting 10min on the nano thin-film, in the process of illumination, the OTS SAMs of exposure area becomes hydroxyl, has obtained-OH/-CH ₃The surface of SAMs patterning; To have again-OH/-CH ₃The absolute methanol solution of 5mM 3-aminopropyl triethoxysilane (APTS) is put in the substrate of SAMs patterning, assembles 3h under the room temperature, promptly obtains-CH ₃/-NH ₂Constructing of-SAMs patterned surface.

3) Cu ₂The preparation of S patterned film: with 0.125g CuSO ₄.5H ₂O, 0.279g EDTA is dissolved in the water of 50mL, forms transparent clear solutions, drips 1M H ₂SO ₄Regulating the pH value is 2.3, adds the Na of 0.124g then ₂S ₂O ₃, after mixing, the substrate of patterning SAMs is put into 70 ℃ of depositions twice of this solution, each 1h.After the substrate taking-up, the flushing of secondary water, ultrasonic cleaning 5min dries up with nitrogen then, at last to Cu ₂The S film is sintering processes under 300 ℃ of nitrogen protections.Can be at TiO ₂The nano thin-film surface obtains patterning nanometer Cu ₂The S film.

Embodiment 2:

1) TiO ₂The preparation of film: at first substrate of glass is immersed the absolute methanol solution of 5mM 3-aminopropyl triethoxysilane (APTS), assemble 3h under the room temperature, clean with absolute methanol, secondary water successively after the taking-up, and dry up with nitrogen; Get 0.06g Ti (SO then ₄) ₂, 0.058g H ₂O ₂Form precursor solution with water, and adjusting pH value is about 1.6; The substrate that then surface is had an APTS places this forerunner's liquid solution, 70 ℃ of deposition 1h.

2)-CH ₃/-NH ₂Constructing of-SAMs patterned surface:

Method is with instance 1.

3) Cu ₂The preparation of S patterned film: with 0.25g CuSO ₄.5H ₂O, 0.558g EDTA is dissolved in the water of 50mL, forms transparent clear solutions, drips 1M H ₂SO ₄Regulating the pH value is 2.0, adds the Na of 0.248g then ₂S ₂O ₃, after mixing, the substrate of patterning SAMs is put into 70 ℃ of depositions twice of this solution, each 0.5h.After the substrate taking-up, the flushing of secondary water, ultrasonic cleaning 5min dries up with nitrogen then, at last to Cu ₂The S film is sintering processes under 250 ℃ of nitrogen protections.

Embodiment 3:

1) TiO ₂The preparation of film:

Method is with instance 1.

2)-CH ₃/-NH ₂Constructing of-SAMs patterned surface:

Method is with instance 1.

3) Cu ₂The preparation of S patterned film: with 0.125g CuSO ₄.5H ₂O, 0.279g EDTA is dissolved in the water of 50mL, forms transparent clear solutions, drips 1M H ₂SO ₄Regulating the pH value is 1.5, adds the Na of 0.248g then ₂S ₂O ₃, after mixing, the substrate of patterning SAMs is put into 70 ℃ of depositions twice of this solution, each 40 minutes.After the substrate taking-up, the flushing of secondary water, ultrasonic cleaning 5min dries up with nitrogen then, at last to Cu ₂The S film is sintering processes under 300 ℃ of nitrogen protections.

Claims

1. patterning preparation method of composite film that strengthens the titanium deoxid film light absorption is characterized in that step is following:

1) TiO ₂The preparation of film: substrate of glass is immersed the absolute methanol solution of 3-aminopropyl triethoxysilane, assemble under the room temperature, clean with absolute methanol, secondary water successively after the taking-up, and dry up with nitrogen; Get Ti (SO then ₄) ₂, H ₂O ₂Form precursor solution with water, and adjusting pH value is about 1.6; The substrate of glass that then surface is had a 3-aminopropyl triethoxysilane places this forerunner's liquid solution, 70～80 ℃ of deposition 20～60min;

2)-CH ₃/-NH ₂Constructing of-SAMs patterned surface: with the made TiO of step (1) ₂Nano thin-film places the hexane solution of octadecyl trichlorosilane, assembles under the room temperature, takes out the back and cleans with n-hexane, and dry up with nitrogen; The TiO that has the octadecyl trichlorosilane then on the surface ₂Place mask and ultraviolet lighting on the nano thin-film, in the process of illumination, the OTS SAMs of exposure area becomes hydroxyl, has obtained-OH/-CH ₃The surface of SAMs patterning; To have again-OH/-CH ₃The absolute methanol solution of 3-aminopropyl triethoxysilane is put in the substrate of SAMs patterning, assembles under the room temperature, obtains-CH ₃/-NH ₂Constructing of-SAMs patterned surface;