CN101339906A

CN101339906A - Preparation process of novel environmental semi-conductor photoelectronic material beta-FeSi2 film

Info

Publication number: CN101339906A
Application number: CNA2008100688618A
Authority: CN
Inventors: 谢泉; 张晋敏; 曾武贤; 梁艳; 肖清泉
Original assignee: Guizhou University
Current assignee: Guizhou University
Priority date: 2008-08-12
Filing date: 2008-08-12
Publication date: 2009-01-07

Abstract

The invention discloses a preparation technique of a novel environmental semiconductor optoelectronics material beta-FeSi2 membrane, and relates to an Fe-Si compound; the method comprises the steps that firstly, a metal Fe film layer with the thickness of 50-150nm is deposited on a Si substrate by adopting the method of magnetron sputtering and then is annealed for 12-18 hours in a vacuum annealing furnace at the temperature of 880-920 DEG C, so that the semiconductor phase beta-FeSi2 membrane in the Fe-Si compound is obtained; as the method of direct current magnetron sputtering is adopted, the thickness of the Fe film deposited on the Si substrate is ensured to be even; the technique is simple, the cost is low, the beta-FeSi2 membrane with large area is easy to prepare, and commercial process is easy to be carried out; furthermore, as the annealing time and the temperature can be strictly controlled, the quality of the products are stable, and the reproduction performance is good.

Description

Novel environmental semi-conductor photoelectronic material beta-FeSi 2The preparation technology of film

Technical field:

The present invention relates to a kind of Fe-Si compound, specifically a kind of novel environmental semi-conductor photoelectronic material beta-FeSi ₂The preparation technology of film and with the β-FeSi of this explained hereafter ₂Film.

Background technology:

Low-temperature stabilization phase β-FeSi in the transition metal silicide Fe-Si compound ₂Be the friendly semi-conducting material of a kind of novel environmental, have good photoelectric characteristic, simultaneously, the component of this material reserves on earth is abundant, nontoxic, and utilizes β-FeSi ₂The technology of film preparation opto-electronic device is compatible mutually with existing silicon integrated circuit technology, therefore, and β-FeSi ₂Film has important use at photoelectricity and thermoelectric field.Block β-FeSi ₂Material generally adopts the sintering process preparation, and film β-FeSi ₂Usually adopt methods such as molecular beam epitaxy, ion beam injection, magnetron sputtering preparation nanometer Fe film on silicon chip earlier, then the nanometer Fe film is heat-treated preparation β-FeSi ₂Film, but adopt molecular beam epitaxy, ion beam injects heating treatment method and prepares β-FeSi ₂Film is owing to complex process cost height, and film speed waits shortcoming slowly, the industrial production cost height, and adopt magnetron sputtering really to have above-mentioned advantage, the industrialization promotion production cost is low.

Summary of the invention:

Because β-FeSi ₂Film environmental friendliness characteristic, collimation tape splicing crack character, with existing si-substrate integrated circuit technology compatibility mutually, make semi-conducting material β-FeSi ₂The exploitation of film, application have crucial value.The objective of the invention is to find a kind of new production low-temperature stabilization phase β-FeSi ₂The method of film, it is simple to make it to have technology, with low cost, is easy to prepare large area uniform film, is easy to realize suitability for industrialized production.

The present invention at first adopts magnetically controlled sputter method to deposit the metal Fe film of a layer thickness 50-150nm on the Si substrate, subsequently 880-920 ℃ of semiconductor phase β-FeSi that annealing obtained in the Fe-Si compound in 12-18 hour in vacuum annealing furnace ₂Film.

The magnetically controlled sputter method of indication of the present invention, be to adopt dc magnetron sputtering method, in sputter, with purity is that 99.95% metallic iron is made target, make substrate with Si (100), the metal Fe film of the about 50-150nm of deposition one layer thickness on Si (100) substrate, the sputtering sedimentation condition: sputtering sedimentation under the room temperature, sputtering parameter is: back of the body end vacuum 2 * 10 ^-5Pa, sputtering pressure 1.0-2.5Pa, Ar throughput 15-30SCCM, sputtering power 80-110W, substrate bias-50V.

The vacuum annealing of indication of the present invention forms β-FeSi ₂The method of film, be with magnetron sputtering deposition at the on-chip Fe film of Si, 880-920 ℃ of annealing obtained the semiconductor phase β-FeSi in the Fe-Si compound in 12-18 hour in vacuum annealing furnace ₂Film, vacuum degree is better than 2 * 10 in the annealing process ^-3Pa.

Operation divides following several steps to carry out

1. substrate and substrate clean

Substrate is selected Si (100) single-chip, single-sided polishing, resistivity 7-13 Ω cm for use.Each ultrasonic cleaning 10 minutes of packing into before the sputtering chamber in acetone, absolute ethyl alcohol and deionized water dries up with nitrogen.

2. the preparation of metal Fe film

Cleaned substrate is placed the sputter Sample Room, after cleaning, backwash sends into sputtering chamber, with purity is that 99.95% metallic iron is made target, make substrate with Si (100) single-chip, adopt dc magnetron sputtering method, at room temperature deposit thickness is the Fe film of 50-150nm on substrate, and splash-proofing sputtering process parameter is as follows: back of the body end vacuum 2 * 10 ^-5Pa, sputtering pressure 1.0-2.5Pa, Ar throughput 15-30SCCM, sputtering power 80-110W, substrate bias-50V, sedimentation time 10 minutes.

3. vacuum annealing forms β-FeSi ₂Film

The Fe film of magnetron sputtering deposition places and adds a cover the molybdenum box, and the molybdenum box is put the uniform temperature zone of vacuum annealing furnace quartz ampoule into, is evacuated to 4.0 * 10 ^-4Be warming up to 880-920 ℃ behind the Pa, be incubated 12-18 hour, naturally cool to room temperature then, vacuum degree is better than 2.0 * 10 in whole annealing process ^-3Pa.The annealing back obtains single phase β-FeSi ₂Film.

Adopt the present invention to produce β-FeSi ₂The technology of film owing to adopt the method for magnetron sputtering, makes that to be deposited on the on-chip iron film thickness of Si even, and technology is simple, and cost is low, is easy to prepare large area film, is easy to realize suitability for industrialized production; The counterdiffusion of atom phase also forms low-temperature stabilization semiconductor phase β-FeSi in the Fe-Si compound ₂Because Fe film deposition in the technology, annealing temperature and annealing time can strictly be controlled, guarantee the steady quality of product of the present invention, good process repeatability uses goods of the present invention nontoxic, harmless to organism and environment for a long time, can be used for the semiconductor photoelectronic device field, as solar cell, Infrared Detectors and light-emitting diode etc.

To film sample, adopt X-ray diffraction (XRD) (Japanese D/MAX-2200 of science) and ESEM (SEM) (S3400N of Hitachi) that crystal structure and surface topography are characterized by method for preparing.See accompanying drawing 1 and accompanying drawing 2.

Description of drawings:

Fig. 1, magnetron sputtering β-FeSi ₂The XRD spectrum of film.

Abscissa is represented the angle of diffraction, and ordinate is represented diffracted intensity, and XRD confirms to have formed single phase semiconductor β-FeSi ₂Film, and have polycrystalline structure.

Fig. 2, magnetron sputtering β-FeSi ₂The SEM image of film.

SEM image show sample crystal grain is the regular polyhedron shape and is distributed in the matrix, and intercrystalline is separated from one another.

Embodiment:

The concrete processing method of embodiment is as follows

1. with each ultrasonic cleaning 10 minutes in acetone, absolute ethyl alcohol and deionized water of Si (100) single-chip (resistivity 7-13 Ω cm) of single-sided polishing, dry up with nitrogen.

2. cleaned substrate is placed the sputter Sample Room, be evacuated to 2 * 10 ^-5Pa, charge into 99.999% pure Ar gas, regulate air pressure and to 7.0Pa, begin the backwash cleaning, subsequently substrate is sent into sputtering chamber, adopt dc magnetron sputtering method on the Si substrate, to deposit the Fe film, keeping Ar air pressure in the sputter procedure is by force 2.0Pa, Ar throughput 20SCCM, sputtering power 80W, substrate bias-50V, spatter beginning deposition Fe film on substrate after 10 minutes in advance, sedimentation time 10 minutes.

3. take out sputtering sedimentation at the on-chip Fe film of Si, place and add a cover the molybdenum box, the molybdenum box is put the uniform temperature zone of vacuum annealing furnace quartz ampoule into, is evacuated to 4.0 * 10 ^-4Be warming up to 900 ℃ behind the Pa, 900 ℃ of insulations 15 hours, naturally cool to room temperature then, vacuum degree is better than 2.0 * 10 in whole annealing process ^-3Pa.The annealing back obtains single phase β-FeSi ₂Film.

Confirm to have obtained single phase β-FeSi after the annealing 4.XRD measure ₂The film (see figure 1).

Because the β-FeSi of this processes ₂Film thickness is even, and area is big, and bigger application and development prospect is arranged, claimed technology of the present invention and with the β-FeSi of this explained hereafter ₂Film product.

Claims

1. novel environmental semi-conductor photoelectronic material beta-FeSi ₂The preparation technology of film is characterized by the metal Fe film that at first adopts magnetically controlled sputter method to deposit a layer thickness 50-150nm on the Si substrate, subsequently 880-920 ℃ of semiconductor phase β-FeSi that annealing obtained in the Fe-Si compound in 12-18 hour in vacuum annealing furnace ₂Film.

2. novel environmental semi-conductor photoelectronic material beta-FeSi according to claim 1 ₂The preparation technology of film, it is characterized in that magnetically controlled sputter method, adopt dc magnetron sputtering method, in sputter, with purity is that 99.95% metallic iron is made target, makes substrate with Si (100), the metal Fe film of deposition one layer thickness 50-150nm on Si (100) substrate, the sputtering sedimentation condition: sputtering sedimentation under the room temperature, sputtering parameter is: back of the body end vacuum 2 * 10 ^-5Pa, sputtering pressure 1.0-2.5Pa, Ar throughput 15-30SCCM, sputtering power 80-110W, substrate bias-50V.

3. novel environmental semi-conductor photoelectronic material beta-FeSi according to claim 1 and 2 ₂The preparation technology of film is characterized in that magnetron sputtering deposition at the on-chip Fe film of Si, 880-920 ℃ of semiconductor phase β-FeSi that annealing obtained in the Fe-Si compound in 12-18 hour in vacuum annealing furnace ₂Film, vacuum degree is better than 2 * 10 in the annealing process ^-3Pa.

4. according to claim 1 or weigh 2 described novel environmental semi-conductor photoelectronic material beta-FeSi ₂The preparation technology of film is characterized in that the β-FeSi that obtains with this technology ₂Film product.

5. novel environmental semi-conductor photoelectronic material beta-FeSi according to claim 3 ₂The preparation technology of film is characterized in that the β-FeSi that obtains with this technology ₂Film product.