CN107644939B - Wide range responds photodetector and preparation method thereof - Google Patents

Wide range responds photodetector and preparation method thereof Download PDF

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CN107644939B
CN107644939B CN201710848505.7A CN201710848505A CN107644939B CN 107644939 B CN107644939 B CN 107644939B CN 201710848505 A CN201710848505 A CN 201710848505A CN 107644939 B CN107644939 B CN 107644939B
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absorbing layer
light absorbing
preparation
photodetector
wide range
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CN107644939A (en
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贾仁需
庞体强
栾苏珍
张玉明
汪钰成
刘银涛
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Xidian University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The present invention relates to a kind of wide range response photodetector and preparation method thereof, the preparation method includes: that (a) chooses Sapphire Substrate；(b) hearth electrode is made in the sapphire substrate surface；(c) light absorbing layer is made on the hearth electrode surface；(d) top electrode is made on the light absorbing layer surface to complete the preparation of the wide range response photodetector.Wide range provided by the invention responds photodetector, and using double-heterostructure to form double potential barrier can effectively reduce leakage current, to greatly improve the device reliability of photodetector.

Description

Wide range responds photodetector and preparation method thereof
Technical field
The present invention relates to semiconductor device design and manufacturing field, in particular to a kind of wide range response photodetector and its Preparation method.
Background technique
Currently, most of photodetectors are the photo-detector diodes based on PN junction, generally can measure ultraviolet to infrared Light region has very big use value, such as in day-old chick to tail cigarette or plumage in the exploitation in military high-tech Yu civilian goods market The airbound target that a large amount of ultraviolet radioactives can be discharged in cigarette carries out real-time detection or effectively tracking, and in infrared region, near infrared from detecting exists The fields such as resource investigation, environmental monitoring, medical diagnosis, night vision imaging suffer from important role.
Based on CH3NH3PbI3Perovskite material be widely used in optical detector, this material is from visible light to close It is infrared to have higher response.However, these photodetectors cannot cover spectral absorption and the ultraviolet spectra of whole visible lights, These limit perovskite material in the application of broader spectrum range.β-Ga2O3 is a kind of with the important of broad prospect of application Functional material, forbidden bandwidth 4.9eV is a kind of semiconductor material with dark purple external characteristics, and the β-Ga2O3 of 200nm is thin Film can reach 80% or more transmitance in UV light region, be widely used in deep ultraviolet light electric explorer.The detection utensil There is high sensitivity, can be applied to the fields such as missile warning, horizon communication and fire hazard monitoring.
The problems such as that there are light absorpting abilities is weak for current photodetector, and spectral response range is narrow.
Summary of the invention
Therefore, a kind of wide range response light electrical resistivity survey is proposed to solve technological deficiency and deficiency, the present invention of the existing technology Survey device and preparation method thereof.
The embodiment provides a kind of preparation methods of wide range response photodetector, comprising:
(a) Sapphire Substrate is chosen；
(b) hearth electrode is made in the sapphire substrate surface；
(c) light absorbing layer is made on the hearth electrode surface；
(d) top electrode is made on the light absorbing layer surface to complete the preparation of the wide range response photodetector.
In one embodiment of the invention, step (b) includes:
(b1) magnetron sputtering technique is utilized, in one metal material of sapphire substrate surface growth regulation；
(b2) under the atmosphere of nitrogen and argon gas, using rapid thermal anneal process, make the Sapphire Substrate and described the One metal material forms Ohmic contact to complete the preparation of the hearth electrode.
In one embodiment of the invention, step (c) includes:
(c1) the first light absorbing layer is made on the hearth electrode surface；
(c2) the second light absorbing layer is made on first light absorbing layer surface；
(c3) third light absorbing layer is made on second light absorbing layer surface.
In one embodiment of the invention, step (c1) includes:
Using magnetron sputtering technique, Ga is grown on the hearth electrode surface2O3Material, as first light absorbing layer.
In one embodiment of the invention, step (c2) includes:
(c21) spin coating precursor solution is prepared；
(c22) precursor solution is spun on first light absorbing layer；
(c23) at a temperature of 90 DEG C, using annealing process, the entire material for including first light absorbing layer is moved back Fire processing forms hydridization perovskite material on the surface of first light absorbing layer, as second light absorbing layer.
In one embodiment of the invention, the hydridization perovskite material is CH3NH3PbI3、CH3NH3PbCl3、 CH3NH3SnI3In any one.
In one embodiment of the invention, step (c3) includes:
Using molecular beam epitaxial process, on second light absorbing layer surface, growth includes the β-of Sn, Si, Al doped chemical Ga2O3Material, as the third light absorbing layer.
In one embodiment of the invention, step (d) includes:
(d1) magnetron sputtering technique, two metal material of growth regulation on third light absorbing layer surface are utilized；
(d2) under the atmosphere of nitrogen and argon gas, using rapid thermal anneal process, make the third light absorbing layer with it is described Second metal material forms Ohmic contact to complete the preparation of the top electrode.
In one embodiment of the invention, first metal material and second metal material be ITO, gold, silver, Nickel, titanium, platinum, palladium, any one in FTO material, or be any several in ITO, gold, silver, nickel, titanium, platinum, palladium, FTO material The alloy of composition.
Another embodiment of the present invention provides a kind of wide ranges to respond photodetector, comprising: Sapphire Substrate, bottom electricity Pole, Ga2O3Light absorbing layer, hydridization perovskite light absorbing layer, β-Ga2O3Light absorbing layer and top electrode；Wherein, told wide range is rung It answers photodetector method as described in any one of above-described embodiment to prepare to be formed.
Compared with prior art, the invention has the following advantages:
1. hydridization perovskite can detect the light of Visible-to-Near InfaRed wave band, and β-Ga2O3 can detect deep ultraviolet to visible Light, the hetero-junctions that the two combines can detect the spectrum from deep ultraviolet to near-infrared, and may be implemented to have complementary advantages；
It can effectively reduce leakage current to form double potential barrier 2. using double-heterostructure, to greatly improve photoelectricity The device reliability of detector；
3. responsiveness with higher and detectivity, while there is low dark current density and high external quantum efficiency.
Detailed description of the invention
Below in conjunction with attached drawing, specific embodiments of the present invention will be described in detail.
Fig. 1 is the preparation method flow chart that a kind of wide range provided in an embodiment of the present invention responds photodetector；
Fig. 2 a- Fig. 2 f is that a kind of wide range of the embodiment of the present invention responds the preparation method schematic diagram of photodetector；
Fig. 3 is the structural schematic diagram that a kind of wide range provided in an embodiment of the present invention responds photodetector.
Specific embodiment
Further detailed description is done to the present invention combined with specific embodiments below, but embodiments of the present invention are not limited to This.
Embodiment 1:
Referring to Figure 1, Fig. 1 is the preparation method process that a kind of wide range provided in an embodiment of the present invention responds photodetector Figure, wherein the preparation method includes:
(a) Sapphire Substrate is chosen；
(b) hearth electrode is made in the sapphire substrate surface；
(c) light absorbing layer is made on the hearth electrode surface；
(d) top electrode is made on the light absorbing layer surface to complete the preparation of the wide range response photodetector.
Preferably, step (b) may include:
(b1) magnetron sputtering technique is utilized, in one metal material of sapphire substrate surface growth regulation；
(b2) under the atmosphere of nitrogen and argon gas, using rapid thermal anneal process, make the Sapphire Substrate and described the One metal material forms Ohmic contact to complete the preparation of the hearth electrode.
Wherein, in step (b), Ti metal layer with a thickness of 50~200nm, the operating power of magnetron sputtering technique is 80W, vacuum degree are 5 × 10-4~6 × 10-3Pa。
Preferably, step (c) may include:
(c1) the first light absorbing layer is made on the hearth electrode surface；
(c2) the second light absorbing layer is made on first light absorbing layer surface；
(c3) third light absorbing layer is made on second light absorbing layer surface.
Further, may include: in step (c1)
Using magnetron sputtering technique, Ga is grown on the hearth electrode surface2O3Material, as first light absorbing layer.
Wherein, in step (c1), Ga2O3First light absorbing layer with a thickness of 150~250nm
Further, may include: in step (c2)
(c21) spin coating precursor solution is prepared；
(c22) precursor solution is spun on first light absorbing layer；
(c23) at a temperature of 90 DEG C, using annealing process, the entire material for including first light absorbing layer is moved back Fire processing forms hydridization perovskite material on the surface of first light absorbing layer, as second light absorbing layer.
Further, may include: in step (c21)
(c211) by CH3NH3I and PbI2It is dissolved in DMF solution；
(c212) at 50 °C, the DMF solution is stirred, to complete the preparation of the spin coating precursor solution.
Wherein, in step (c211), CH3NH3The quality of I is 0.415g, PbI2Quality be 1.223g, DMF solution is 4mL。
Preferably, step (c3) may include:
Using molecular beam epitaxial process, on second light absorbing layer surface, growth includes the β-of Sn, Si, Al doped chemical Ga2O3Material, as the third light absorbing layer.
Optionally, step (d) may include:
(d1) magnetron sputtering technique, two metal material of growth regulation on third light absorbing layer surface are utilized；
(d2) under the atmosphere of nitrogen and argon gas, using rapid thermal anneal process, make the third light absorbing layer with it is described Second metal material forms Ohmic contact to complete the preparation of the top electrode.
Wherein, in step (d1), the operating power of magnetron sputtering technique is 60~80W, and vacuum degree is 5 × 10-4~6 × 10-3Pa。
Preferably, first metal material and second metal material are ITO, gold, silver, nickel, titanium, platinum, palladium, FTO Any one in material, or be the alloy of any several compositions in ITO, gold, silver, nickel, titanium, platinum, palladium, FTO material；Into one Step ground, first metal material and second metal material are that golden material can achieve optimum efficiency.
The present embodiment, hydridization perovskite can detect the light of Visible-to-Near InfaRed wave band, and β-Ga2O3 can detect it is dark purple Visible light is arrived outside, and the hetero-junctions that the two combines can detect the spectrum from deep ultraviolet to near-infrared, and it is mutual that advantage may be implemented It mends；Using double-heterostructure, to form double potential barrier, leakage current can effectively reduce, to greatly improve photodetector Device reliability；Responsiveness and detectivity with higher, while there is low dark current density and high external quantum efficiency.
Embodiment 2:
A- Fig. 2 f referring to figure 2., Fig. 2 a- Fig. 2 f are that a kind of wide range of the embodiment of the present invention responds the preparation of photodetector Method schematic diagram, the preparation method include the following steps:
Step 1 chooses Sapphire Substrate 201, as shown in Figure 2 a.
Step 2, using magnetron sputtering technique, sputter Ti material on 201 surface of Sapphire Substrate；In the gas of nitrogen and argon gas Under atmosphere, using rapid thermal anneal process, Sapphire Substrate 201 and Ti material is made to form Ohmic contact to complete hearth electrode 202 Preparation is as shown in Figure 2 b.
Step 3, using magnetron sputtering technique, grow Ga on 202 surface of hearth electrode2O3, such as the first light absorbing layer 203 Shown in Fig. 2 c.
Step 4, preparation spin coating precursor solution；Precursor solution is spun to 203 surface of the first light absorbing layer；? At a temperature of 90 DEG C, using annealing process, the entire material for including the first light absorbing layer 203 is made annealing treatment, in the first light The surface of absorbed layer 203 forms CH3NH3PbI3Film, as the second light absorbing layer 204,
As shown in Figure 2 d.
Step 5, using molecular beam epitaxial process, on 204 surface of the second light absorbing layer, growth includes Sn, Si, Al doping member β-the Ga of element2O3Material, as third light absorbing layer 205, as shown in Figure 2 e.
Step 6, using magnetron sputtering technique, in Ga2O3205 surface of third light absorbing layer grows Au material；In nitrogen and argon Under the atmosphere of gas, using rapid thermal anneal process, third light absorbing layer is made to form Ohmic contact with the Au material to complete to push up The preparation of electrode, as shown in figure 2f.
Embodiment three
Referring to figure 3., Fig. 3 is the structural schematic diagram that a kind of wide range provided in an embodiment of the present invention responds photodetector. The photodetector is made of the above-mentioned preparation method as shown in Fig. 2 a- Fig. 2 f.Specifically, the photodetector includes: Sapphire Substrate 301, hearth electrode 302, Ga2O3Light absorbing layer 303, hydridization perovskite light absorbing layer 304, β-Ga2O3Light absorbing layer 305 and top electrode 306.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention Protection scope.

Claims (6)

1. a kind of preparation method of wide range response photodetector characterized by comprising
(a) Sapphire Substrate is chosen；
(b) hearth electrode is made in the sapphire substrate surface；
Step (b) includes:
(b1) magnetron sputtering technique is utilized, in one metal material of sapphire substrate surface growth regulation；
(b2) under the atmosphere of nitrogen and argon gas, using rapid thermal anneal process, make the Sapphire Substrate and first gold medal Belong to material and forms Ohmic contact to complete the preparation of the hearth electrode；
(c) light absorbing layer is made on the hearth electrode surface；
Step (c) includes:
(c1) magnetron sputtering technique is utilized, grows Ga on the hearth electrode surface2O3Material, as the first light absorbing layer；
(c2) hydridization perovskite material is prepared on first light absorbing layer surface using solution spin-coating method, as the second light absorption Layer；
(c3) molecular beam epitaxial process is utilized, growth includes the β-of Sn, Si, Al doped chemical on second light absorbing layer surface Ga2O3Material, as third light absorbing layer；
(d) magnetron sputtering technique is utilized, two metal material of growth regulation makes institute as top electrode on third light absorbing layer surface It states third light absorbing layer and the top electrode forms Ohmic contact to complete the preparation of top electrode, to complete the wide range response The preparation of photodetector.
2. preparation method according to claim 1, which is characterized in that step (c2) includes:
(c21) spin coating precursor solution is prepared；
(c22) precursor solution is spun on first light absorbing layer；
(c23) at a temperature of 90 DEG C, using annealing process, the entire material for including first light absorbing layer is carried out at annealing Reason forms hydridization perovskite material on the surface of first light absorbing layer, as second light absorbing layer.
3. preparation method according to claim 1, which is characterized in that the hydridization perovskite material is CH3NH3PbI3、 CH3NH3PbCl3And CH3NH3SnI3In any one.
4. preparation method according to claim 1, which is characterized in that step (d) includes:
(d1) magnetron sputtering technique, two metal material of growth regulation on third light absorbing layer surface are utilized；
(d2) under the atmosphere of nitrogen and argon gas, using rapid thermal anneal process, make the third light absorbing layer and described second Metal material forms Ohmic contact to complete the preparation of the top electrode.
5. the preparation method according to claim 4, which is characterized in that first metal material and second metal material Material is ITO, gold, silver, nickel, titanium, platinum, palladium, any one in FTO material, or is ITO, gold, silver, nickel, titanium, platinum, palladium, FTO material The alloy of any several compositions in material.
6. a kind of wide range responds photodetector characterized by comprising Sapphire Substrate, hearth electrode, Ga2O3Light absorbing layer, Hydridization perovskite light absorbing layer, β-Ga2O3Light absorbing layer and top electrode；Wherein, the wide range response photodetector is by right It is required that 1~5 described in any item methods prepare to be formed.
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