CuO/Se composite film

Abstract

Disclosed is a CuO/Se composite film, in which Se with low melting point (221° C.) and strong photosensitivity is introduced into CuO, providing the film with fewer defects and excellent optical, electrical and photoelectric properties. In the preparation method of the invention, Se is introduced into CuO and melted by low-temperature annealing, and then the molten Se can infiltrate CuO to eliminate or reduce defects in the CuO film such as voids and dangling bonds, thereby improving optical, electrical and photoelectric properties of the film and overcoming the shortcomings that CuO has poor crystallinity, high melting point and is decomposed at a high temperature.

Claims

1. A CuO/Se composite film, comprising a CuO—Se composite; wherein the CuO—Se composite comprises at least one of CuSe.sub.2, CuSe and Cu.sub.2Se; and the CuO/Se composite film comprises 10-60 at. % of Cu, 10-60 at. % of O and 10-60 at. % of Se, where O is the same as Cu in atomic percent (at. %).

2. The CuO/Se composite film of claim 1, wherein the CuO/Se composite film comprises 20-40 at. % of Cu and 20-50 at. % of Se.

3. The CuO/Se composite film of claim 1, wherein the CuO/Se composite film contains Cu.sub.2O, CuSe.sub.2, and optionally CuSe and Cu.sub.2Se.

4. The CuO/Se composite film of claim 1, wherein the CuO/Se composite film is further doped with Si, Fe or Ge.

5. The CuO/Se composite film of claim 2, wherein the CuO/Se composite film is further doped with Si, Fe or Ge.

6. The CuO/Se composite film of claim 3, wherein Si, Fe or Ge doped in the CuO/Se composite film is 3-10 at. %.

7. The CuO/Se composite film of claim 4, wherein Si, Fe or Ge doped in the CuO/Se composite film is 3-10 at. %.

8. The CuO/Se composite film of claim 1, wherein the film is prepared by a magnetron sputtering method comprising: depositing a crude CuO/Se composite film on a substrate by co-sputtering of CuO and Se; and then annealing the crude CuO/Se composite film at 150-300° C. in air or nitrogen for 1-3 min to produce the CuO/Se composite film; or depositing a CuO film on a glass substrate using magnetron sputtering; depositing a Se film on the CuO film by thermal evaporation; and then annealing the CuO film and the Se film deposited thereon in air or nitrogen at 150-300° C. for 10-60 min to produce the CuO/Se composite film.

9. The CuO/Se composite film of claim 1, wherein the film is prepared by a chemical solution method comprising: mixing a CuO powder and a Se powder uniformly in a molar ratio of 1:2-3 by grinding; adding the mixed powder to dimethyl sulfoxide; stirring the reaction mixture at 50-70° C. for 6-10 h; spin-coating the reaction mixture on a substrate; and annealing the substrate at 150-200° C. for 5-10 min to prepare the CuO/Se composite film.

10. The CuO/Se composite film of claim 7, wherein the substrate is any one of a monocrystalline silicon wafer, an ordinary glass, a quartz glass, an indium tin oxide conductive glass and a fluorine-doped tin oxide conductive glass.

11. The CuO/Se composite film of claim 8, wherein the substrate is any one of a monocrystalline silicon wafer, an ordinary glass, a quartz glass, an indium tin oxide conductive glass and a fluorine-doped tin oxide conductive glass.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows an X-ray diffraction pattern characterizing the structure of a CuO/Se composite film prepared in Example 1.

(2) FIG. 2 is a scanning electron micrograph (SEM) showing the CuO/Se composite film prepared in Example 1.

(3) FIG. 3 is an absorption spectrum of the CuO/Se composite film prepared in Example 1.

(4) FIG. 4 is a graph showing the photocurrent decay of the CuO/Se composite film prepared in Example 1 with a carrier diffusion distance.

DETAILED DESCRIPTION OF EMBODIMENTS

(5) The present invention will be further described in detail below with reference to the accompanying drawings and embodiments, however, these embodiments are not intended to limit the invention.

Example 1

(6) An ordinary glass substrate was cleaned sequentially in acetone, ethanol and deionized water under ultrasonication for 10 min, dried with nitrogen and then placed in a magnetron sputtering deposition chamber. The deposition chamber was vacuumed to 2×10.sup.−4 Pa using a mechanical pump and a turbomolecular pump, and a distance between the glass substrate and a target material was adjusted to 6 cm. Then the glass substrate was heated to 200° C. An argon vent valve was opened to fill the deposition chamber with argon. Simultaneously, a mass flow meter was opened to control the argon flow rate to 30 sccm. The pressure of the deposition chamber was adjusted to 0.6 Pa. CuO and Se were co-sputtered onto the rotated substrate under a sputtering power of 60 W for 30 min to deposit a composite film on the glass substrate, where the deposited composite film had a thickness of 4 μm. After that, the deposited composite film was naturally cooled to room temperature and annealed at 200° C. in the air for 1 min to obtain a CuO/Se composite film.

(7) The CuO/Se composite film prepared herein was confirmed by a Hall-effect measurement to have a p-type conductivity, a carrier concentration of 2.05×10.sup.19 cm.sup.−3, a mobility of 98 cm.sup.2V.sup.−1s.sup.−1 and a resistivity of 3.12×10.sup.−3 Ωcm. It can be seen from the X-ray diffraction pattern in FIG. 1 that in the CuO/Se composite film, CuO was amorphous and a part of Se was nano-crystalline and estimated to have an average crystalline size of 48 nm through the Debye-Scherrer equation. Moreover, CuSe.sub.2 nanocrystals were observed in the film with an average crystalline size of 44 nm, indicating that the film was a composite non-crystal/nanocrystal film. However, neither CuO nor Se was crystallized in the film without annealing. The atomic percentages of Cu, O and Se in the CuO/Se composite film were measured by energy dispersive X-ray spectroscopy (EDX) to be about 30%, 32% and 38%, respectively. FIG. 2 was a scanning electron micrograph (SEM) which showed that a surface of the CuO/Se composite film was formed from particles of 10-30 nm in size. The absorption spectrum of the CuO/Se composite film was measured using an ultraviolet-visible-near-infrared spectrophotometer, and as shown in FIG. 3, the CuO/Se composite film prepared herein showed strong light adsorption (an average absorption rate was close to 80%) throughout the solar spectrum (250-2500 nm). The photocurrent scanning method was used to directly measure the photocurrent decay of the CuO/Se composite film with carrier diffusion distance, and the results were shown in FIG. 4. The photo-generated carrier diffusion length L.sub.D of the CuO/Se composite film was calculated to be 3.147 mm according to the exponential decay equation I=I.sub.0exp(−L/L.sub.D), which was longer than the carrier diffusion length of the best p-type monocrystalline silicon (1.95 mm), and far longer than the carrier diffusion length of the organic-inorganic hybrid perovskite materials which were currently widely-researched (for example, a single crystal CH.sub.3NH.sub.3PbI.sub.3 had a carrier diffusion length of 0.32 mm and a polycrystalline film had a carrier diffusion length of 0.014 mm). These characteristics indicated that the CuO/Se composite film of the invention was an excellent electro-optical material.

Example 2

(8) In this embodiment, CuO, Se and Si were co-sputtered to prepare a CuO/Se composite film according to the conditions of Example 1, where the atomic percentages of Cu, O, Se and Si in the CuO/Se composite film were 30%, 30%, 36% and 4%, respectively. The CuO/Se composite film prepared herein also showed strong absorption to light throughout the solar spectrum (250-2500 nm) with an average absorption rate close to 80%. The photo-generated carrier diffusion length L.sub.D of the CuO/Se composite film was directly measured by photocurrent scanning method to be 3.124 mm.

Example 3

(9) A CuO film was deposited by magnetron sputtering on a glass substrate according to the conditions of Example 1, and then a Se film was deposited on the CuO film by conventional thermal evaporation. Then the two layers of films were annealed at 220° C. in the air for 10 min to produce a CuO/Se composite film.

Example 4

(10) 0.4 g (5 mmol) of CuO powder and 0.34 g (10 mmol) of Se powder were ground and uniformly mixed, added to 3 mL of DMSO and stirred at 60° C. for 8 h. The reaction mixture was spin-coated on a glass substrate at 1000 rpm. Then the substrate was annealed at 150° C. for 10 min to prepare a CuO/Se composite film.