CN102064206A - Multi-component gradient-doping GaN UV (Ultraviolet) light cathode material structure and manufacture method thereof - Google Patents

Multi-component gradient-doping GaN UV (Ultraviolet) light cathode material structure and manufacture method thereof Download PDF

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CN102064206A
CN102064206A CN2010105651335A CN201010565133A CN102064206A CN 102064206 A CN102064206 A CN 102064206A CN 2010105651335 A CN2010105651335 A CN 2010105651335A CN 201010565133 A CN201010565133 A CN 201010565133A CN 102064206 A CN102064206 A CN 102064206A
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multicomponent
doping
ultraviolet light
cathode material
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常本康
李飙
徐源
杜玉杰
王晓晖
杜晓晴
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Nanjing University of Science and Technology
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Abstract

The invention provides a reflection-type GaN UV (Ultraviolet) light cathode material structure and a manufacture method thereof. The structure comprises a substrate, an involuntarily doping AlN buffer layer, a p-type GaxAI1-xN multi-component mix-crystal photoelectric emission layer and a Cs or Cs /O active layer, wherein the involuntarily doping AlN buffer layer grows on the substrate; the p-type GaxAI1-xN multi-component mix-crystal photoelectric emission layer epitaxially grows on the AlN buffer layer; and the Cs or Cs /O active layer is absorbed on the front surface of the p-type GaxAI1-xN multi-component mix-crystal photoelectric emission layer and has the thickness of an nm order of magnitude. By adopting the multi-component and gradient-doping photoelectric emission layer, the structure increases the escape depth of photonexcited electrons in the emission layer and improves the possibility for emitting the electrons in the emission layer into vacuum so as to improve the whole quantum efficiency of the GaN UV light cathode and acquire higher UV sensibility.

Description

Multicomponent, grade doping GaN ultraviolet light photo-cathode material structure and preparation method thereof
Technical field
The invention belongs to the ultraviolet detection material technical field, be specifically related to reflective ultraviolet light photo-cathode material structure that a kind of based semiconductor material epitaxy technology, semi-conducting material doping techniques and ultra high vacuum surface activation technology combine and preparation method thereof.
Background technology
In recent years, along with improving and the development of ultra high vacuum technique of GaN material preparation technology, p type doping techniques, GaN ultraviolet light photo negative electrode is just becoming a kind of ultraviolet light photo negative electrode of novel high-performance.The surface of this negative electrode has negative electron affinity (Negative Electron Affinity, NEA), be that the surface vacuum energy level of negative electrode is lower than in the body energy level at the bottom of the conduction band, therefore the optical excitation electronics only need run to the surface in the body, just can be transmitted into vacuum by tunnelling, need not the potential barrier that superfluous kinetic energy removes to overcome material surface, the escape probability of optical excitation electronics is increased greatly, and for cold electron emission, therefore have the quantum efficiency height, secretly launch little, emitted electron energy and distribute and distinct advantages such as concentrate.Its quantum efficiency generally＞24%, the quantum efficiency that is much higher than traditional ultraviolet light photo negative electrode 10% is (as cesium telluride, has the positron affinity, Positive Electron Affinity, PEA), and, GaN material energy gap is～3.4eV, the following ultra-violet radiation of response 400nm is typical " day is blind " material, has good capability of resistance to radiation.
GaN ultraviolet light photo negative electrode can be worked under reflective-mode or transmission mode.When light from the incident of negative electrode front surface and electronics is reflective-mode work during surface emitting in the past also; When light from the rear surface incident of negative electrode and electronics is transmission mode work during surface emitting in the past.Reflective GaN ultraviolet light photo-cathode material structure generally comprise from bottom to top backing material (adopting sapphire usually), epitaxial growth at the AlN resilient coating on the substrate, be grown in the p type GaN photoemissive material on the resilient coating and the active coating of low work function element absorption.Wherein photoemissive layer adopts the p type evenly to mix, owing to have concentration difference in emission layer surface and the body, is moved to body surface with the diffusion form by the electronics of incident light from the valence to the conduction band.In the transport process some electronics repeatedly with the lattice collisions off-energy after by compound, can't overflow, thereby reduce electronics emission quantity, cause cathode quantum efficiency lower.
Find by literature search, adopt varying doping structure photoemissive layer can improve the optical excitation electronics from the body to the transport capability of body surface, increased the electronics escaped quantity, thereby obtained higher quantum efficiency.Photoemissive layer is taked suitable varying doping structure, can in the emission layer body, produce and help the internal electric field of electronics to apparent motion, make the electronics that is energized into conduction band at the diffusion motion of in the process of apparent motion, both having deposited in vivo and concentration difference between body surface causes, can under the effect of internal electric field, do drift motion again, diffusion adds that the motion mode of drift can increase the probability that electronics arrives cathode surface, and then the electronics escape probability increases quantum efficiency acquisition raising.But still less than depths optical excitation electronics effusion ratio in the emission layer body, the optical excitation electron escape depth still has the space of lifting.
Summary of the invention
Technical problem solved by the invention is to provide multicomponent, grade doping GaN ultraviolet light photo-cathode material structure of a kind of further raising optical excitation electron escape depth and preparation method thereof.
The technical solution that realizes the object of the invention is: a kind of multicomponent, grade doping GaN ultraviolet light photo-cathode material structure, this material structure are followed successively by AlN resilient coating, the p type Ga of substrate, involuntary doping from bottom to top xAl 1-xN multicomponent mixed crystal photoemissive layer and Cs or Cs/O active coating.
A kind of method of making multicomponent, grade doping GaN ultraviolet light photo-cathode material structure may further comprise the steps:
Step 1, at the upper surface of the Sapphire Substrate of twin polishing, by the grow AlN resilient coating of involuntary doping of the epitaxial growth technology of semi-conducting material;
Step 2, the p type doping process by epitaxial growth technology and III-V group iii v compound semiconductor material, growing p-type Ga on the AlN resilient coating that step 1 obtains xAl 1-xN multicomponent mixed crystal photoemissive layer is as photoemissive material;
Remaining inorganic attachment in step 3, the surperficial grease of the cathode material that utilizes chemical cleaning removal step 2 to obtain and the course of processing; Then it is sent in the ultra-high vacuum system, material surface is added thermal purification, make material surface reach the atom level clean level;
Step 4, at above-mentioned p type GaN material surface by activation technology absorption monolayer Cs or multi-layer C s/O, to form Cs or Cs/O active coating, finally prepare multicomponent, grade doping structure GaN ultraviolet light photo negative electrode with negative electron affinity.
The present invention compared with prior art, its remarkable advantage: 1) the present invention proposes the reflective ultraviolet light photo-cathode material structure that a kind of based semiconductor material epitaxy technology, semi-conducting material doping techniques and ultra high vacuum surface activation technology combine, and this structure adopts Ga xAl 1-xN multicomponent and grade doping photoemissive layer, increased the escape depth of optical excitation electronics in the emission layer, improve the interior electronics of emission layer and be transmitted into the probability of vacuum, thereby improved the overall quantum efficiency of GaN ultraviolet light photo negative electrode, obtained higher ultraviolet sensitivity; 2) because Ga xAl 1-xThe energy gap of N multicomponent mixed crystal emissive layer materials is respective change with the change of x, and is adjustable corresponding to the ultraviolet threshold of response; 3) this ultraviolet light photo-cathode material structure can be used as a kind of cold electron source of ultraviolet efficiently, is applied to devices such as microwave tube, circular accelerator meter; Also can be used as the light-sensitive element of active ultraviolet detector, be applied to fields such as ultraviolet alarm.
Below in conjunction with accompanying drawing the present invention is described in further detail.
Description of drawings
Fig. 1 is the layer structural representation of GaN ultraviolet light photo-cathode material of the present invention.
Fig. 2 is a GaN ultraviolet light photo-cathode material fundamental diagram of the present invention.
Embodiment
In conjunction with Fig. 1, Fig. 2, a kind of multicomponent of the present invention, grade doping GaN ultraviolet light photo-cathode material structure, this material structure are followed successively by AlN resilient coating 2, the p type Ga of substrate 1, involuntary doping from bottom to top xAl 1-xN multicomponent mixed crystal photoemissive layer 3 and Cs or Cs/O active coating 4.Described substrate 1 is the sapphire of twin polishing.AlN resilient coating 2 epitaxial growths of described involuntary doping are on substrate 1, and thickness is between 10-200nm.Described p type Ga xAl 1-x3 epitaxial growths of N multicomponent mixed crystal photoemissive layer are on AlN resilient coating 2, and thickness is between 100-200nm, and the doping content scope is 10 16-10 19Cm -3, doping content is from reducing Ga successively to the surface in the body xAl 1-xThe proportional control parameter x serves as the growth starting point with the AlN resilient coating in the N multicomponent mixed crystal, fades to 1 from 0.Described Cs or Cs/O active coating 4 are adsorbed on p type Ga xAl 1-xOn the front surface of N multicomponent mixed crystal photoemissive layer 3, thickness is at the nm order of magnitude.
A kind of method of making multicomponent, grade doping GaN ultraviolet light photo-cathode material structure may further comprise the steps:
Step 1, at the upper surface of the Sapphire Substrate 1 of twin polishing, by the grow AlN resilient coating 2 of involuntary doping of the epitaxial growth technology of semi-conducting material; The thickness of the AlN resilient coating 2 of described involuntary doping is 10-200nm.
Step 2, the p type doping process by epitaxial growth technology and III-V group iii v compound semiconductor material, growing p-type Ga on the AlN resilient coating 2 that step 1 obtains xAl 1-xN multicomponent mixed crystal photoemissive layer 3 is as photoemissive material; Described p type Ga xAl 1-xThe thickness of N multicomponent mixed crystal photoemissive layer 3 is 100-200nm, and its doping content scope is 10 16-10 19Cm -3And doping content is from reducing described Ga successively to the surface in the body xAl 1-xThe proportional control parameter x serves as the growth starting point with the AlN resilient coating in the N multicomponent mixed crystal, fades to 1 from 0.
Remaining inorganic attachment in step 3, the surperficial grease of the cathode material that utilizes chemical cleaning removal step 2 to obtain and the course of processing; Then it is sent in the ultra-high vacuum system, material surface is added thermal purification, make material surface reach the atom level clean level; Temperature when material surface is added thermal purification is 700-900 ℃, and be 10-30 minute heating time.
Step 4, at above-mentioned p type GaN material surface by activation technology absorption monolayer Cs or multi-layer C s/O, to form Cs or Cs/O active coating 4, finally prepare multicomponent, grade doping structure GaN ultraviolet light photo negative electrode with negative electron affinity.
In conjunction with Fig. 2, the operation principle of reflection type GaN ultraviolet light photo-cathode material structure of the present invention is: the mode of operation of this ultraviolet light photo-cathode material is reflective, and promptly ultraviolet light goes into to shine from the front surface of negative electrode, and process active coating 4 is by p type Ga xAl 1-xN multicomponent mixed crystal photoemissive layer 3 absorbs, after absorbing photon, photoemissive layer 3 obtains energy, when incident photon energy during greater than the energy gap (Eg=3.4eV) of GaN material, the electronics that is in valence band just can transit to conduction band becomes free electron, and these free electrons add that by diffusion the motion mode of drift arrives cathode surface and is transmitted into vacuum.Ga xAl 1-xThe N multiple component structure has improved the escape probability of emission layer depths optical excitation electronics on the one hand, has increased the adjustment to the ultraviolet response wave length on the other hand.After electronics is transmitted into vacuum, added forceful electric power and pressed collection, and exported with the photoelectric current form by adding Acquisition Circuit.The ultraviolet light of incident is strong more, p type Ga xAl 1-xThe photon energy that N multicomponent mixed crystal photoemissive layer 3 absorbs is just many more, and the photoelectric current of output is also just big more.
Below in conjunction with embodiment the present invention is done further detailed description:
Embodiment 1: as shown in Figure 1, a kind of reflection type GaN ultraviolet light photo-cathode material structure, this material structure are from bottom to top by substrate 1 (as sapphire), involuntary doped with Al N resilient coating 2, p type Ga xAl 1-xN multicomponent mixed crystal photoemissive layer 3 and Cs or Cs/O active coating 4 constitute; Wherein, AlN resilient coating 2 epitaxial growths of involuntary doping are on substrate layer 1, and thickness is 50nm; P type Ga xAl 1-x3 epitaxial growths of N multicomponent mixed crystal photoemissive layer are on aforementioned AlN resilient coating 2, and thickness is 120nm, and doping content is followed successively by 1 * 10 18, 4 * 10 17, 2 * 10 17With 6 * 10 16, by reducing gradually to body surface in the body, the proportional control parameter x serves as the growth starting point with the AlN resilient coating in the mixed crystal, fades to 1 from 0; Cs active coating 4 is adsorbed on p type Ga by the ultra high vacuum activation technology xAl 1-xOn the front surface of N multicomponent mixed crystal photoemissive layer 3, thickness is a monoatomic layer.
Embodiment 2: with implement 1 different be that the thickness of AlN resilient coating is 100nm; P type Ga xAl 1-x3 epitaxial growths of N multicomponent mixed crystal photoemissive layer are on aforementioned AlN resilient coating 2, and thickness is 120nm, and doping content is followed successively by 1 * 10 18, 4 * 10 17, 2 * 10 17With 6 * 10 16, by reducing gradually to body surface in the body, the proportional control parameter x serves as the growth starting point with the AlN resilient coating in the mixed crystal, fades to 1 from 0; Cs active coating 4 is adsorbed on p type Ga by the ultra high vacuum activation technology xAl 1-xOn the front surface of N multicomponent mixed crystal photoemissive layer 3, thickness is a monoatomic layer.
Embodiment 3: with implement 1 different be that the thickness of AlN resilient coating is 100nm; P type Ga xAl 1-x3 epitaxial growths of N multicomponent mixed crystal photoemissive layer are on aforementioned AlN resilient coating 2, and thickness is 150nm, and doping content is followed successively by 1 * 10 18, 4 * 10 17, 2 * 10 17With 6 * 10 16, by reducing gradually to body surface in the body, the proportional control parameter x serves as the growth starting point with the AlN resilient coating in the mixed crystal, fades to 1 from 0; Cs active coating 4 is adsorbed on p type Ga by the ultra high vacuum activation technology xAl 1-xOn the front surface of N multicomponent mixed crystal photoemissive layer 3, thickness is a monoatomic layer.
Embodiment 4: with implement 1 different be that the thickness of AlN resilient coating is 10nm; P type Ga xAl 1-x3 epitaxial growths of N multicomponent mixed crystal photoemissive layer are on aforementioned AlN resilient coating 2, and thickness is 100nm, and doping content is followed successively by 1 * 10 18, 4 * 10 17, 2 * 10 17With 6 * 10 16, by reducing gradually to body surface in the body, the proportional control parameter x serves as the growth starting point with the AlN resilient coating in the mixed crystal, fades to 1 from 0; Cs active coating 4 is adsorbed on p type Ga by the ultra high vacuum activation technology xAl 1-xOn the front surface of N multicomponent mixed crystal photoemissive layer 3, thickness is a monoatomic layer.
Embodiment 5: with implement 1 different be that the thickness of AlN resilient coating is 200nm; P type Ga xAl 1-x3 epitaxial growths of N multicomponent mixed crystal photoemissive layer are on aforementioned AlN resilient coating 2, and thickness is 200nm, and doping content is followed successively by 1 * 10 18, 4 * 10 17, 2 * 10 17With 6 * 10 16, by reducing gradually to body surface in the body, the proportional control parameter x serves as the growth starting point with the AlN resilient coating in the mixed crystal, fades to 1 from 0; Cs active coating 4 is adsorbed on p type Ga by the ultra high vacuum activation technology xAl 1-xOn the front surface of N multicomponent mixed crystal photoemissive layer 3, thickness is a monoatomic layer.
The manufacture method of above-mentioned reflection type GaN ultraviolet light photo-cathode material structure is:
At first, upper surface in the Sapphire Substrate 1 of twin polishing, epitaxial growth technology by semi-conducting material is (as the metal organic-matter chemical gas deposition, Metalorganic Chemical Vapor Deposition, MOCVD and molecular beam epitaxy, Molecular Beam Epitaxy, MBE etc.) the AlN resilient coating 2 of the involuntary doping of the described thickness of growth; Secondly, by the p type doping process of identical epitaxial growth technology and III-V group iii v compound semiconductor material, the described thickness of growth, doping content scope are 10 on AlN resilient coating 2 again 16-10 19Cm -3P type Ga xAl 1-xN multicomponent mixed crystal photoemissive layer 3 is as photoemissive material; Once more, the cathode material that epitaxial growth obtained adopts chemical cleaning (as adopting 2: 2: 1 the concentrated sulfuric acid, H 2O 2Mixed liquor cleaning material surface with deionized water) remaining inorganic attachment in the grease on removal emission layer surface and the course of processing; Then it is sent in the ultra-high vacuum system and heat,, make material surface reach the atom level clean level as under 710 ℃, material surface being carried out 30 minutes the thermal purification that adds; At last, the p type Ga that is obtaining xAl 1-xN multicomponent mixed crystal material surface to form Cs or Cs/O active coating, is finally prepared the GaN ultraviolet light photo negative electrode with negative electron affinity by activation technology absorption monolayer Cs or multi-layer C s/O.
The present invention is not limited to the restriction of described enforcement to the thickness of resilient coating, photoelectric emission layer thickness and active coating, as long as the simple change of being done on the structure of technical solution of the present invention all falls into protection scope of the present invention.

Claims (9)

1. a multicomponent, grade doping GaN ultraviolet light photo-cathode material structure is characterized in that this material structure is followed successively by AlN resilient coating (2), the p type Ga of substrate (1), involuntary doping from bottom to top xAl 1-xN multicomponent mixed crystal photoemissive layer (3) and Cs or Cs/O active coating (4).
2. multicomponent according to claim 1, grade doping GaN ultraviolet light photo-cathode material structure is characterized in that described substrate (1) is the sapphire of twin polishing.
3. multicomponent according to claim 1, grade doping GaN ultraviolet light photo-cathode material structure is characterized in that, AlN resilient coating (2) epitaxial growth of described involuntary doping is on substrate (1), and thickness is between 10-200nm.
4. multicomponent according to claim 1, grade doping GaN ultraviolet light photo-cathode material structure is characterized in that, described p type Ga xAl 1-xN multicomponent mixed crystal photoemissive layer (3) epitaxial growth is on AlN resilient coating (2), and thickness is between 100-200nm, and the doping content scope is 10 16-10 19Cm -3, doping content is from reducing Ga successively to the surface in the body xAl 1-xThe proportional control parameter x serves as the growth starting point with the AlN resilient coating in the N multicomponent mixed crystal, fades to 1 from 0.
5. multicomponent according to claim 1, grade doping GaN ultraviolet light photo-cathode material structure is characterized in that, described Cs or Cs/O active coating (4) are adsorbed on p type Ga xAl 1-xOn the front surface of N multicomponent mixed crystal photoemissive layer (3), thickness is at the nm order of magnitude.
6. a method of making the described multicomponent of claim 1, grade doping GaN ultraviolet light photo-cathode material structure is characterized in that, may further comprise the steps:
Step 1, at the upper surface of the Sapphire Substrate (1) of twin polishing, by the grow AlN resilient coating (2) of involuntary doping of the epitaxial growth technology of semi-conducting material;
Step 2, by the p type doping process of epitaxial growth technology and III-V group iii v compound semiconductor material, go up growing p-type Ga at the AlN resilient coating (2) that step 1 obtains xAl 1-xN multicomponent mixed crystal photoemissive layer (3) is as photoemissive material;
Remaining inorganic attachment in step 3, the surperficial grease of the cathode material that utilizes chemical cleaning removal step 2 to obtain and the course of processing; Then it is sent in the ultra-high vacuum system, material surface is added thermal purification, make material surface reach the atom level clean level;
Step 4, at above-mentioned p type GaN material surface by activation technology absorption monolayer Cs or multi-layer C s/O, to form Cs or Cs/O active coating (4), finally prepare multicomponent, grade doping structure GaN ultraviolet light photo negative electrode with negative electron affinity.
7. according to the method for the described manufacturing multicomponent of claim 6, grade doping GaN ultraviolet light photo-cathode material structure, it is characterized in that the thickness of the AlN resilient coating (2) of involuntary doping in the step 1 is 10-200nm.
8. according to the method for the described manufacturing multicomponent of claim 6, grade doping GaN ultraviolet light photo-cathode material structure, it is characterized in that p type Ga in the step 2 xAl 1-xThe thickness of N multicomponent mixed crystal photoemissive layer (3) is 100-200nm, and its doping content scope is 10 16-10 19m -3And doping content is from reducing described Ga successively to the surface in the body xAl 1-xThe proportional control parameter x serves as the growth starting point with the AlN resilient coating in the N multicomponent mixed crystal, fades to 1 from 0.
9. according to the method for the described manufacturing multicomponent of claim 6, grade doping GaN ultraviolet light photo-cathode material structure, it is characterized in that the temperature when in the step 3 material surface being added thermal purification is 700-900 ℃, be 10-30 minute heating time.
CN2010105651335A 2010-11-30 2010-11-30 Multi-component gradient-doping GaN UV (Ultraviolet) light cathode material structure and manufacture method thereof Pending CN102064206A (en)

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CN103123885A (en) * 2013-01-24 2013-05-29 中国电子科技集团公司第五十五研究所 Variable doping structure of transmission-type photoelectric cathode material for enhancing thermal stability
CN103295855A (en) * 2013-05-29 2013-09-11 南京理工大学 Index-doped reflecting-type GaAs (gallium arsenide) photoelectric cathode and production method thereof
CN103779436A (en) * 2014-01-13 2014-05-07 南京理工大学 Transmission-type AlGaN ultraviolet photocathode and preparation method thereof
CN104752117A (en) * 2015-03-03 2015-07-01 东华理工大学 NEA electron source for vertically emitting AlGaAs/GaAs nanowires
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CN107393787A (en) * 2017-07-24 2017-11-24 中国电子科技集团公司第五十五研究所 The blue green light sensitive transmission formula GaAlAs negative electrodes of Al composition gradient gradual changes
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CN101866976A (en) * 2010-05-21 2010-10-20 重庆大学 Transmission-type GaN ultraviolet photocathode based on varied-doping structure and manufacturing method
CN101866977A (en) * 2010-06-25 2010-10-20 重庆大学 Transmission-type GaN ultraviolet photocathode based on composition graded buffer layer

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CN103123885A (en) * 2013-01-24 2013-05-29 中国电子科技集团公司第五十五研究所 Variable doping structure of transmission-type photoelectric cathode material for enhancing thermal stability
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CN103779436B (en) * 2014-01-13 2017-01-04 南京理工大学 Transmission-type AlGaN ultraviolet light photo negative electrode and preparation method thereof
CN103779436A (en) * 2014-01-13 2014-05-07 南京理工大学 Transmission-type AlGaN ultraviolet photocathode and preparation method thereof
CN104752117A (en) * 2015-03-03 2015-07-01 东华理工大学 NEA electron source for vertically emitting AlGaAs/GaAs nanowires
CN105449066A (en) * 2015-12-07 2016-03-30 南京理工大学 Superlattice graded buffer layer transmissive AlGaN ultraviolet cathode and preparation method therefor
CN107393787A (en) * 2017-07-24 2017-11-24 中国电子科技集团公司第五十五研究所 The blue green light sensitive transmission formula GaAlAs negative electrodes of Al composition gradient gradual changes
CN108933181A (en) * 2018-07-09 2018-12-04 广西大学 The preparation method of transmission-type nanometer suede InAlN base PETE solar battery structure and its cathode
CN110379866A (en) * 2019-06-27 2019-10-25 南京理工大学 Solar battery based on vacuum separation formula p-n junction N-shaped varying doping GaN base anode
CN110379866B (en) * 2019-06-27 2021-04-06 南京理工大学 Solar cell based on vacuum separation type p-n junction n-type variable doping GaN-based anode
CN112687500A (en) * 2021-01-27 2021-04-20 南阳理工学院 Variable spectrum GaAlAs photoelectric emission material and preparation method thereof
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Application publication date: 20110518