CN101333672A - Electrochemical method for preparing high oriented cuprous bromide semiconductor film - Google Patents

Abstract

The invention discloses an electrochemical preparation method of a high-oriented cuprous bromide semiconductor film, comprising the following steps that: 1) an ITO conductive glass or a stainless steel is rinsed with acetone and is then cleaned by deionized water in an ultrasonic cleanser, then the ITO conductive glass or the stainless steel is placed in a 10 percent nitric acid solution for activation, and is finally cleaned by the deionized water; 2) a copper bromide solution whose pH value is adjusted by 2mol/L HBr or 0.1mol/L NaOH solution for getting an electrolyte; and 3) the ITO conductive glass or the stainless steel serves as a working electrode, a platinum electrode serves as a counter electrode, and a calomel electrode serves as a reference electrode and is put into the electrolyte together for electrodeposition. The electrodeposition cathode electric potential ranges from 0.05V to -0.4V relative to the saturated calomel electrode, the deposition electric quantity ranges from 0.01 to 10-coulomb, and the deposition temperature is 25 to 80DEG C. The method has the advantages of simple equipment, low temperature, low cost, and easy control of orientation and appearance of the film. The method is applied to scientific research as well as mass industrial production.

Description

A kind of electrochemical preparation method of high oriented cuprous bromide semiconductor film

Technical field

The present invention relates to the preparation of semiconductor material thin film, relate in particular to the electrochemical preparation method of the high oriented film of cuprous bromide semiconductor material.

Background technology

The CuBr crystal is the wide band gap semiconducter that has the good ionophore of very low local electronic conductivity and have unusual photoluminescent property.It has three kinds of phases, all is good Cu ⁺Conductor has the γ-phase of zincblende lattce structure below 385 ℃; β-the phase that has Wurzite structure in the time of 385～469 ℃; And the α-phase that when 469～488 ℃ (fusing point), has face-centred cubic structure, its Cu ⁺Ion is random distribution CuBr.γ-phase CuBr electroconductibility size depends mainly on and the deviation of desirable stoichiometric composition and the quantity of introducing impurity element when the preparation sample, and the conductivity of α-phase and β-mutually has then that intrinsic value is that determine almost to have nothing to do with preparation method sample.CuBr has been used for the catalyzer of organic synthesis, battery, gas sensor and laser apparatus.Developed some at present based on gaseous techniques and prepared the method for CuBr film, as frequency of radio magnetic sputtering method, molecular beam epitaxy etc.Yet these methods require high temperature, high vacuum, and complex apparatus and strict experimental arrangement have hindered their widespread usage greatly.

Certain methods based on liquid phase also has been used for studying the nanocrystalline growth of CuBr, and is synthetic etc. as sol-gel method and hydro-thermal.Section's (Gedanken) usefulness ultrasonic electrochemical method of etc.ing in red heptan have tensio-active agent in the presence of obtained the nanocrystal ((Hai Si (I.Haas), section's pellet heptan (A.Gedanken), Chem.Mater.18 (2006) 1184) of CuBr.The method that Ke Nashi (Knauth) etc. has developed a kind of electrochemical anodic oxidation Cu sheet has obtained CuBr the film ((Ben Dahan (M.Bendahan) of random orientation, such restrain (P.Lauque), (plucked instrument heptan (J.L.Seguin), (elder brother's that) K.Aguir, Ke Nashi (P.Knauth), Sensors andActuators B-Chem., 95 (2003) 170).

Summary of the invention

The objective of the invention is to overcome the deficiencies in the prior art, a kind of electrochemical preparation method of high oriented cuprous bromide semiconductor film is provided.

Comprise the steps:

1) uses acetone rinsing ITO conductive glass or stainless steel 2～3 times, with deionized water ITO conductive glass or stainless steel are placed on again and clean 10～30 minutes in the ultrasonic cleaner, then ITO conductive glass or stainless steel are placed in 10% the salpeter solution and activate 10～30 seconds, use washed with de-ionized water at last;

2) the cupric bromide solution of 0.05～2 mol is 1～5.0 with the HBr of 2mol/L or the NaOH solution adjusting pH value of 0.1mol/L, obtains electrolytic solution;

3) ITO conductive glass or stainless steel are as working electrode, platinum electrode is as counter electrode, mercurous chloride electrode is put into electrolytic solution together as reference electrode and is carried out galvanic deposit, with respect to the galvanic deposit cathode potential of saturated calomel electrode be 0.05V～-0.4V, the deposition electric weight is 0.01～10 coulomb, 25～80 ℃ of depositing temperatures.

The present invention has the advantages that equipment is simple, cost is low, sedimentation rate is fast, the material growth temperature is low, can operate at normal temperatures and pressures.Prepare CuBr film uniform-dimension evenly, good crystallinity, along＜111 the crystalline axis direction preferred growth.The CuBr crystal of high orientation at room temperature presents the intensive FREE EXCITON EMISSION IN FORWARD.This product is expected at catalyzer, battery, and aspects such as gas sensor and laser apparatus obtain to use widely.

Description of drawings

Fig. 1 is the X-ray diffractogram ((JCPDS 82-2118) is consistent with standard diffraction card) of CuBr film;

Fig. 2 is the sem photograph of cuprous bromide CuBr product.

Fig. 3 is the room temperature photoluminescence spectra of CuBr film;

Fig. 4 is the sem photograph of cuprous bromide CuBr product.

Embodiment

The reaction process of the inventive method can be expressed as follows:

Cu ²⁺+e→Cu ⁺ (1)

Cu ⁺+Br ^-→CuBr (2)

Embodiment 1

1) with acetone rinsing ITO conductive glass 2 times, with deionized water the ITO conductive glass is placed in the ultrasonic cleaner again and cleaned 10 minutes, then the ITO conductive glass was placed in 10% the salpeter solution activation 10 seconds, use washed with de-ionized water at last;

2) the cupric bromide solution of 0.05 mol is 1 with the HBr of 2mol/L or the NaOH solution adjusting pH value of 0.1mol/L, obtains electrolytic solution;

3) the ITO conductive glass is as working electrode, platinum electrode is as counter electrode, and mercurous chloride electrode is put into electrolytic solution together as reference electrode and carried out galvanic deposit, is 0.05VV with respect to the galvanic deposit current potential of saturated calomel electrode, the deposition electric weight is 0.01 coulomb, 25 ℃ of depositing temperatures.

To being deposited on the structural characterization of the CuBr film on the ITO conductive glass, has the γ-phase CuBr with zincblende lattce structure of [111] preferred orientation through field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD) etc. for growing perpendicular to the ITO conductive glass.And this film has the photic blue spectrum of very strong room temperature.X-ray diffraction Fig. 1 shows [111] orientation that having of CuBr is very strong.

Embodiment 2

1) with acetone rinsing stainless steel 3 times, with deionized water stainless steel is placed in the ultrasonic cleaner again and cleaned 30 minutes, then stainless steel was placed in 10% the salpeter solution activation 30 seconds, use washed with de-ionized water at last;

2) the cupric bromide solution of 2 mol is 5.0 with the HBr of 2mol/L or the NaOH solution adjusting pH value of 0.1mol/L, obtains electrolytic solution;

3) stainless steel is as working electrode, and platinum electrode is as counter electrode, and mercurous chloride electrode is put into electrolytic solution together as reference electrode and carried out galvanic deposit, with respect to the galvanic deposit current potential of saturated calomel electrode is-0.4V, and the deposition electric weight is 10 coulombs, 80 ℃ of depositing temperatures.

To being deposited on the structural characterization of the CuBr film on the ITO conductive glass, has the γ-phase CuBr with zincblende lattce structure of [111] preferred orientation through field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD) etc. for growing perpendicular to the ITO conductive glass.And this film has the photic blue spectrum of very strong room temperature.Scanning electron microscope Fig. 2 shows that the CuBr film is smoothly fine and close.

Embodiment 3

1) with acetone rinsing ITO conductive glass 3 times, spend an ionized water again and the ITO conductive glass is placed in the ultrasonic cleaner cleaned 15 1 minutes, then the ITO conductive glass was placed in 10% the salpeter solution activation 30 seconds, use washed with de-ionized water at last;

2) the cupric bromide solution of 0.1 mol is 3.0 with the HBr of 2mol/L or the NaOH solution adjusting pH value of 0.1mol/L, obtains electrolytic solution;

3) the ITO conductive glass is as working electrode, and platinum electrode is as counter electrode, and mercurous chloride electrode is put into electrolytic solution together as reference electrode and carried out galvanic deposit, with respect to the galvanic deposit current potential of saturated calomel electrode is-0.2V, and the deposition electric weight is 2 coulombs, 25 ℃ of depositing temperatures.

To being deposited on the structural characterization of the CuBr film on the ITO conductive glass, has the γ-phase CuBr with zincblende lattce structure of [111] preferred orientation through field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD) etc. for growing perpendicular to the ITO conductive glass.And this film has the photic blue spectrum of very strong room temperature.The photic fluorogram of room temperature sees that Fig. 3 shows that CuBr has the photic blue light performance of very strong room temperature.

Embodiment 4

1) with acetone rinsing ITO conductive glass 3 times, with deionized water the ITO conductive glass is placed in the ultrasonic cleaner again and cleaned 30 minutes, then ITO conductive glass or stainless steel were placed in 10% the salpeter solution activation 30 seconds, use washed with de-ionized water at last;

2) the cupric bromide solution of 0.05～2 mol is 2.0 with the HBr of 2mol/L or the NaOH solution adjusting pH value of 0.1mol/L, obtains electrolytic solution;

3) the ITO conductive glass is as working electrode, and platinum electrode is as counter electrode, and mercurous chloride electrode is put into electrolytic solution together as reference electrode and carried out galvanic deposit, is-0.3 with respect to the galvanic deposit current potential of saturated calomel electrode, and the deposition electric weight is 5 coulombs, 80 ℃ of depositing temperatures.

To being deposited on the structural characterization of the CuBr film on the ITO conductive glass, has the γ-phase CuBr with zincblende lattce structure of [111] preferred orientation through field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD) etc. for growing perpendicular to the ITO conductive glass.And this film has the photic blue spectrum of very strong room temperature.Sem photograph Fig. 4 shows that temperature has certain influence to the pattern of CuBr film.

Claims (1)

1. the electrochemical preparation method of a high oriented cuprous bromide semiconductor film is characterized in that comprising the steps:

1) uses acetone rinsing ITO conductive glass or stainless steel 2～3 times, with deionized water ITO conductive glass or stainless steel are placed on again and clean 10～30 minutes in the ultrasonic cleaner, then ITO conductive glass or stainless steel are placed in 10% the salpeter solution and activate 10～30 seconds, use washed with de-ionized water at last;

2) the cupric bromide solution of 0.05～2 mol is 1～5.0 with the HBr of 2mol/L or the NaOH solution adjusting pH value of 0.1mol/L, obtains electrolytic solution;

3) ITO conductive glass or stainless steel are as working electrode, platinum electrode is as counter electrode, mercurous chloride electrode is put into electrolytic solution together as reference electrode and is carried out galvanic deposit, with respect to the galvanic deposit cathode potential of saturated calomel electrode be 0.05V～-0.4V, the deposition electric weight is 0.01～10 coulomb, 25～80 ℃ of depositing temperatures.

Images