CN106435479A - Nano semiconductor photorefractive thin film material and preparation method thereof - Google Patents
Nano semiconductor photorefractive thin film material and preparation method thereof Download PDFInfo
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- CN106435479A CN106435479A CN201610959284.6A CN201610959284A CN106435479A CN 106435479 A CN106435479 A CN 106435479A CN 201610959284 A CN201610959284 A CN 201610959284A CN 106435479 A CN106435479 A CN 106435479A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0623—Sulfides, selenides or tellurides
Abstract
The invention discloses a nano semiconductor photorefractive thin film material and a preparation method thereof. The nano semiconductor photorefractive thin film material comprises a metal thin film and a lead chalcogenide compound thin film, wherein one surface of the metal thin film is in contact with one surface of the lead chalcogenide compound thin film; and the work function of a metal of the metal thin film is greater than or equal to the electron affinity of a lead chalcogenide compound thin film semiconductor, or a schottky junction is formed on the contact interface of the metal thin film and the lead chalcogenide compound thin film. The preparation method comprises the steps of growing a layer of transparent metal thin film on a substrate, and then growing a layer of a lead chalcogenide compound thin film semiconductor material on the metal thin film. By the connection of the metal thin film to the lead chalcogenide compound thin film and the formation of the schottky junction on the interface of the metal thin film and the lead chalcogenide compound thin film, a built-in electric field is formed in the thin films, so that movement and redistribution of photon-generated carriers can be realized without an external electric field, and the aim of application of a photorefractive material is completely fulfilled.
Description
Technical field
The present invention relates to a kind of Nano semiconductor Preset grating thin-film material and preparation method thereof.
Background technology
Photorefractive effect (photorefractive effect) refers to a kind of special photoinduction variations in refractive index phenomenon.
Carrier (electronics or hole) in the shallow well that the impurity being strapped in some crystal or organic matter or defect are formed by incident light
Eject, if light intensity is uneven, photoexcitation carrier will be migrated by processes such as diffusions, and result is in medium
In photoinduction electric field occurs.Photoinduction electric field produces variations in refractive index by the electrooptic effect of medium again.But variations in refractive index is not
It is instant generation, and need certain setup time；Even the low light level, as long as irradiation time long enough also can produce obvious light
Sell off effect；Photorefractive effect could be produced only in medium in the uneven light field of spatial distribution, and once light folding occurs
Become, can keep in dark for a long time.The material with photorefractive effect is photorefractive material, because it has in light irradiation
Under there is the property of photoinduced refractive index change, thus can be used for the fields such as holographic recording, phase-modulation, integrated optics.
Current photorefractive material is mainly crystalline material and organic film material.Crystal includes mineral crystal, such as titanium ore
Barium titanate (the BaTiO of structure3), potassium niobate (KNbO3) and potassium tantalate-niobate (KTN) etc..Tungsten bronze structure photorefractive crystal has niobic acid
Barium sodium (BNN), strontium barium niobate (SBN) and potassium sodium strontium barium niobate (KNSBN) etc.；Semiconductor crystal, such as GaAs:EL2、InP:Fe、
CdTe:V etc.；Organic crystal and film, such as PVK, COANP:TCNQ etc..
But, the shortcoming that existing photorefractive material exists has：First, crystal growth cycles are slow, complex process, apply size
Greatly, processing trouble, consuming material are many；2nd, need extra electric field that photo-generated carrier is redistributed, so that refractive index occurs
Change.
Content of the invention
It is an object of the invention to provide a kind of Nano semiconductor Preset grating thin-film material and preparation method thereof, existing to overcome
There is the defect of technology.
For achieving the above object, the technical scheme is that：
Application in photorefractive material for the chalcogenide thin film of lead.
By research, the present invention finds that the chalcogenide thin film of lead has faint photorefractive effect first.
The chalcogen compound of heretofore described lead is the compound of sulphur series elements and lead element, and its chemical formula is PbA,
Wherein, A is sulphur series elements, such as sulphur, selenium, tellurium etc..
Preferably, the chalcogenide thin film of described lead is narrow gap semiconductor film.
Heretofore described band gap is the difference of the energy of peak of the minimum point of conduction band and valence band, also referred to as energy gap.Band
Gap is considered as wide band gap semiconducter more than 3eV, such as GaN, SiN and ZnO, and what band gap was less than 3eV is exactly narrow band gap.
Preferably, the thickness of the chalcogenide thin film of described lead is 100-300nm.
Preferably, the chalcogen compound of described lead is vulcanized lead (PbS), lead selenide (PbSe) or lead telluride (PbTe).
A kind of Nano semiconductor Preset grating thin-film material, including the chalcogenide thin film of metallic film and lead, described gold
Belong to film with the chalcogenide thin film of lead while contact, wherein, the work function of the metal of described metallic film is big
Electron affinity energy in the chalcogenide thin film semiconductor equal to described lead.
A kind of Nano semiconductor Preset grating thin-film material, including the chalcogenide thin film of metallic film and lead, described gold
Belong to film with the chalcogenide thin film of lead while contact, wherein, described metallic film is chalcogenide with described lead
The contact interface of compound film forms schottky junction.
The present invention is combined with metallic film by the chalcogenide thin film of lead and forms schottky junction in contact interface, can increase
Strong photorefractive effect.The chalcogenide thin film of lead is n-type semiconductor, when the work function of metal is partly led more than or equal to N-shaped
During the affinity of body, form schottky junction, i.e. built in field at both interfaces.Lead with the metallic film that meets this requirement and partly
The composite construction of body thin film preparation, absorbs photon energy by semiconductor film material under light illumination and produces electron hole, these light
Raw carrier redistributes under built in field effect, thus bringing the change of semiconductor film material refractive index.
Preferably, substrate, the another side of described metallic film and substrate contact are also included.
It is further preferred that described substrate is BaF2Substrate.BaF2Substrate is few to light absorbs, transparent wavelength range width.Printing opacity
Wave-length coverage 0.2-25 micron, light transmittance more than 92%.
Preferably, the chalcogenide thin film of described lead is narrow gap semiconductor film.
Preferably, the thickness of the chalcogenide thin film of described lead is 100-300nm.
Preferably, the chalcogen compound of described lead is vulcanized lead (PbS), lead selenide (PbSe) or lead telluride (PbTe).
Preferably, the thickness of described metallic film is 10-30nm.
Preferably, the material of described metallic film be gold, silver, copper, iron, aluminium, cobalt, nickel, zinc, chromium, molybdenum, titanium, tungsten, vanadium, tin,
Beryllium.
A kind of preparation method of above-mentioned Nano semiconductor Preset grating thin-film material, in the metal of Grown layer of transparent
Film, then grows the chalcogenide thin film semi-conducting material of one layer of lead on described metallic film.
In the present invention, the metallic film in Grown layer of transparent is to prepare metallic film in the one side of substrate, its system
Preparation Method can be vacuum evaporation, magnetron sputtering, laser splash or molecular beam epitaxy etc..
The chalcogenide thin film semi-conducting material growing one layer of lead in the present invention on metallic film is in metallic film
One side prepare the chalcogenide thin film semi-conducting material of lead, its preparation method can also be vacuums evaporation, magnetron sputtering, sharp
Light sputtering or molecular beam epitaxy etc..
Described be evaporated in vacuo as under vacuum conditions, METAL HEATING PROCESS being melted to evaporation, metallic atom condenses in substrate table
The method that face forms very thin metallic film.
Described magnetron sputtering is as target cathode using Coating Materials, using argon ion bombardment target, produces cathodic sputtering,
Target atom is splashed to a kind of coating technique forming sedimentary on workpiece.
Described laser splash is in target (Coating Materials) surface by high power pulsed laser focussing force, is target material surface
Produce high temperature and ablation, and produce HTHP plasma (T further>104K), this plasma orientation local essence,
On workpiece, deposition forms film.
Described molecular beam epitaxy is a kind of new technology preparing monocrystal thin films, and it is in suitable substrate and suitable condition
Under, along the method for backing material crystalline axis direction successively growing film.
Preferably, the method in the metallic film of Grown layer of transparent is magnetron sputtering method.
It is further preferred that the step of described magnetically controlled sputter method is specially：Washes of absolute alcohol BaF2Substrate, adopts
99.99% metallic target, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas, sputtering chamber operating pressure 0.45Pa, sputtering voltage
340V, electric current 80mA, sputter rate 0.08-0.19nm/s, sputtering time 60-125s.
Preferably, the method growing the chalcogenide thin film semi-conducting material of one layer of lead on described metallic film is magnetic
Control sputtering method.
It is further preferred that the step of described magnetically controlled sputter method is specially：On metallic film, sputtering lead is chalcogenide
Compound film, the chalcogen compound target of the lead using 99.99%, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas, sputtering chamber
Operating pressure 0.45Pa, sputtering power 20W, sputter rate 0.09-0.12nm/s, sputtering time 835-1100s.
Application in holographic recording, phase-modulation or integrated optics for the above-mentioned Nano semiconductor Preset grating thin-film material.
Beneficial effects of the present invention are：
1. the present invention adopts the chalcogenide thin film of lead as photorefractive material, preparation technology is easy easily, preparation when
Between short.
2. the present invention is engaged with the chalcogenide thin film of lead using metallic film, and in the chalcogen with metallic film and lead
The interface of compound film forms schottky junction, thus forming built in field in film, photo-generated carrier being moved and divides
Cloth, is not required to extra electric field, is fully achieved the application purpose of photorefractive material.
3. the present invention is using forming the composite construction that is combined of schottky junction with metal it was found that this big class semiconductive thin film
The photorefractive effect of material, is the simple miniaturized application of photorefractive material, there is provided extensively prospect.
4. the present invention using with metal formed the preparation method is simple of composite construction that schottky junction is combined easily, prepare when
Between short, easily realize industrialized production.
Brief description
Fig. 1 be the embodiment of the present invention 1 preparation Nano semiconductor Preset grating thin-film material (BaF2/ Cu/PbTe film)
Structural representation；
Fig. 2 is the BaF of the embodiment of the present invention 1 preparation2The Preset grating refractive-index grating occurring in/Cu/PbTe membrane structure
Photo；
Fig. 3 tests light path schematic diagram for two-beam coupling；
Fig. 4 reads light path schematic diagram for two-beam coupling experiment refractive-index grating.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment the invention will be further described.
Embodiment 1
Washes of absolute alcohol BaF2Substrate, using 99.99% copper target, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas,
Sputtering chamber operating pressure 0.45Pa, sputtering voltage 300V, electric current 80mA, sputter rate 0.08nm/s, sputtering time 125s, thus
In BaF2Prepare on substrate 10nm about transparent copper film.
Using 99.99% PbTe target, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas, sputtering chamber operating pressure
0.45Pa, sputtering power 20W, sputter rate 0.09nm/s, sputtering time 1100s, thus prepare on transparent copper film
100nm about PbTe film, that is, obtain BaF2/ Cu/PbTe film.
Material structure after preparation is as shown in Figure 1.Using the BaF to preparation for the two-beam coupling experiment2/ Cu/PbTe film enters
The inspection of row photorefractive effect, as shown in Fig. 2 two-beam coupling experiment is the most effective means of inspection photorefractive effect.
Two-beam coupling tests concrete steps：Two-beam coupling experiment light path is as shown in Figure 3.
1. the write of refractive-index grating.Wavelength is the Nd of 0.19mW for 532nm power:YAG laser, through half-wave plate, space
Become collimated light beam after filter plate and lens, two-beam be divided into by beam splitter, two-beam is incident upon sample surfaces with 14 degree of angles,
Two-beam interferes in sample interior, due to photorefractive effect thus forming refractive-index grating.
2. blocked with photochopper light path 1 incident light when, light output can also be detected in the laser power meter of this light path,
Calculate diffraction efficiency and reach 9%.
3. the reading of refractive-index grating.Read light path as shown in Figure 4.
The refractive-index grating of write in 1 is positioned in Fig. 4 light path, by the Nd for 532nm for the wavelength:The power of YAG laser
It is down to relatively low level, refractive-index grating is read by reconstruction of hologram principle, is taken pictures by CCD (charge coupled cell) and obtain figure
2 photos.
The BaF preparing can be will become apparent from from Fig. 22/ Cu/PbTe film has obvious photorefractive effect, i.e. diffraction
Efficiency is up to 9%.
Embodiment 2
Washes of absolute alcohol BaF2Substrate, using 99.99% PbTe target, sputtering chamber is evacuated down to 5 × 10-4Pa, fills
Argon gas, sputtering chamber operating pressure 0.45Pa, sputtering power 20W, sputter rate 0.09nm/s, sputtering time 1100s, thus
BaF2Prepare on substrate 100nm about PbTe film, obtain final product BaF2/ PbTe film.
By the BaF to preparation for the two-beam coupling experiment2/ PbTe film carries out the inspection of photorefractive effect, BaF2/ PbTe is thin
Film has weaker photorefractive effect.Weaker photorefractive effect refers to：Shoot photo by CCD (charge coupled cell) to obtain
Diffraction efficiency of grating very low, less than 0.1%, in addition the refractive-index grating striped read of index path is tested very by two-beam coupling
Weak.BaF manufactured in the present embodiment2The diffraction efficiency of grating of/PbTe film is very low, and only 0.05%.
Embodiment 3
Washes of absolute alcohol BaF2Substrate, using 99.99% gold target, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas,
Sputtering chamber operating pressure 0.45Pa, sputtering voltage 340V, electric current 80mA, sputter rate 0.19nm/s, sputtering time 60s, thus
In BaF2Prepare on substrate 10nm about transparent gold film.
Using 99.99% PbTe target, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas, sputtering chamber operating pressure
0.45Pa, sputtering power 20W, sputter rate 0.09nm/s, sputtering time 1000s, thus prepare on transparent silverskin
100nm about PbTe film, that is, obtain BaF2/ Au/PbTe film.
Embodiment 4
Washes of absolute alcohol BaF2Substrate, using 99.99% copper target, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas,
Sputtering chamber operating pressure 0.45Pa, sputtering voltage 300V, electric current 80mA, sputter rate 0.08nm/s, sputtering time 125s, thus
In BaF2Prepare on substrate 10nm about transparent copper film.
Using 99.99% PbSe target, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas, sputtering chamber operating pressure
0.45Pa, sputtering power 20W, sputter rate 0.1nm/s, sputtering time 1000s, thus prepare on transparent copper film
100nm about PbSe film, that is, obtain BaF2/ Cu/PbSe film.
Embodiment 5
Washes of absolute alcohol BaF2Substrate, using 99.99% copper target, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas,
Sputtering chamber operating pressure 0.45Pa, sputtering voltage 300V, electric current 80mA, sputter rate 0.08nm/s, sputtering time 125s, thus
In BaF2Prepare on substrate 10nm about transparent copper film.
Using 99.99% PbS target, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas, sputtering chamber operating pressure
0.45Pa, sputtering power 20W, sputter rate 0.12nm/s, sputtering time 835s, thus prepare on transparent copper film
100nm about PbS film, that is, obtain BaF2/ Cu/PbS film.
Embodiment 6
Washes of absolute alcohol BaF2Substrate, using 99.99% aluminium target, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas,
Sputtering chamber operating pressure 0.45Pa, sputtering voltage 300V, electric current 80mA, sputter rate 0.15nm/s, sputtering time 67s, thus
In BaF2Prepare on substrate 10nm about transparent aluminium film.
Using 99.99% PbTe target, sputtering chamber is evacuated down to 5 × 10-4Pa, applying argon gas, sputtering chamber operating pressure
0.45Pa, sputtering power 20W, sputter rate 0.09nm/s, sputtering time 1100s, thus prepare in transparent aluminium film
100nm about PbTe film, that is, obtain BaF2/ Al/PbTe film.
According to the two-beam coupling experimental procedure in embodiment 1, Preset grating inspection is carried out to thin-film material prepared by embodiment 3-9
Survey, wherein, the thin-film material of embodiment 3-5 preparation has obvious photorefractive effect；And the thin-film material tool of embodiment 6 preparation
There is weaker photorefractive effect.
The electron affinity energy of PbTe, PbSe and PbS is as shown in table 1.
Table 1
| PbTe | PbSe | PbS | |
| Electron affinity energy (eV) | 4.6eV | 4.2eV | 4.35eV |
Common metal work function is as shown in table 2.
Table 2
| Gold | Silver | Copper | Iron | Aluminium | Cobalt | Nickel | Zinc | |
| Work function (eV) | 5.1 | 4.26 | 4.65 | 4.5 | 4.28 | 5.0 | 5.15 | 4.33 |
| Chromium | Molybdenum | Titanium | Tungsten | Vanadium | Tin | Beryllium | Palladium | |
| Work function (eV) | 4.5 | 4.6 | 4.33 | 4.55 | 4.3 | 4.42 | 4.98 | 5.12 |
Shown by embodiment 1-6 and table 1-2, the chalcogenide thin film material of lead has weaker photorefractive effect,
When the electron affinity energy of the chalcogen compound that the work function of metal is more than or equal to lead, form schottky junction at both interfaces,
The photorefractive effect of the chalcogenide thin film material of lead can greatly be improved.
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to invention protection domain
Restriction, one of ordinary skill in the art should be understood that, on the basis of technical scheme, those skilled in the art are not required to
The various modifications that creative work to be paid can be made or deformation are still within the scope of the present invention.
Claims (10)
1. application in photorefractive material for the chalcogenide thin film of lead.
2. apply as claimed in claim 1, it is characterized in that, the chalcogenide thin film of described lead is that narrow gap semiconductor is thin
Film；
Or, the thickness of the chalcogenide thin film of described lead is 100-300nm；
Or, the chalcogen compound of described lead is vulcanized lead, lead selenide or lead telluride.
3. a kind of Nano semiconductor Preset grating thin-film material, is characterized in that, including the chalcogenide thin film of metallic film and lead,
Described metallic film with the chalcogenide thin film of lead while contact, wherein, the work(of the metal of described metallic film
Function is more than or equal to the electron affinity energy of the chalcogenide thin film semiconductor of described lead.
4. a kind of Nano semiconductor Preset grating thin-film material, is characterized in that, including the chalcogenide thin film of metallic film and lead,
Described metallic film with the chalcogenide thin film of lead while contact, wherein, described metallic film and described lead
The contact interface of chalcogenide thin film forms schottky junction.
5. the Nano semiconductor Preset grating thin-film material as described in claim 3 or 4, is characterized in that, also include substrate, described gold
Belong to another side and the substrate contact of film；
Preferably, described substrate is BaF2Substrate.
6. the Nano semiconductor Preset grating thin-film material as described in claim 3 or 4, is characterized in that, the chalcogenide of described lead
Thing film is narrow gap semiconductor film；
Or, the thickness of the chalcogenide thin film of described lead is 100-300nm；
Or, the thickness of described metallic film is 10-30nm.
7. the Nano semiconductor Preset grating thin-film material as described in claim 3 or 4, is characterized in that, the chalcogenide of described lead
Thing is vulcanized lead, lead selenide or lead telluride；
Or, the material of described metallic film is gold, silver, copper, iron, aluminium, cobalt, nickel, zinc, chromium, molybdenum, titanium, tungsten, vanadium, tin, beryllium.
8. a kind of preparation method of the arbitrary described Nano semiconductor Preset grating thin-film material of claim 3-7, is characterized in that,
The metallic film of Grown layer of transparent, then grows the chalcogenide thin film half of one layer of lead on described metallic film
Conductor material.
9. preparation method as claimed in claim 8, is characterized in that, in the method for the metallic film of Grown layer of transparent
For magnetron sputtering method.
Or, the method growing the chalcogenide thin film semi-conducting material of one layer of lead on described metallic film is magnetron sputtering
Method.
10. the arbitrary described Nano semiconductor Preset grating thin-film material of claim 3-7 is in holographic recording, phase-modulation or integrated
Application in optics.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108359951A (en) * | 2018-03-13 | 2018-08-03 | 天津科技大学 | The method that directional nano pillar array structure PbTe films are prepared using magnetron sputtering |
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| US20070189359A1 (en) * | 2002-06-12 | 2007-08-16 | Wei Chen | Nanoparticle thermometry and pressure sensors |
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| CN108359951A (en) * | 2018-03-13 | 2018-08-03 | 天津科技大学 | The method that directional nano pillar array structure PbTe films are prepared using magnetron sputtering |
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