CN107579126A - A kind of ultraviolet detector and preparation method thereof - Google Patents
A kind of ultraviolet detector and preparation method thereof Download PDFInfo
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- CN107579126A CN107579126A CN201710779638.3A CN201710779638A CN107579126A CN 107579126 A CN107579126 A CN 107579126A CN 201710779638 A CN201710779638 A CN 201710779638A CN 107579126 A CN107579126 A CN 107579126A
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- zinc oxide
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Abstract
The invention discloses a kind of ultraviolet detector and preparation method thereof, the preparation method includes：One substrate is provided；Zinc oxide film is formed in the substrate surface；Fluorine moditied processing is carried out to the surface of the zinc oxide film so that the zinc oxide film has fluorine-containing functional group；The electrode of preset pattern structure is formed on the surface of the zinc oxide film, the electrode surface has In grains；Wherein, the functional group is used to increase the adsorbance and the rate of adsorption to oxygen.Technical solution of the present invention can optimize these three characteristics of responsiveness, dark current and the response time of ultraviolet detector simultaneously.
Description
Technical field
The present invention relates to technical field of semiconductor device, in particular, is related to a kind of ultraviolet detector and its making side
Method.
Background technology
Ultraviolet detection technology can be used for military communication, Missile Plume detection, fire alarm, environmental monitoring, biological effect etc.
Aspect, militarily or on civilian all it is widely used.At present, the ultraviolet detector that oneself puts it into commercial operation mainly has
Silicon detector, photomultiplier and semiconductor detector.Silicon substrate ultraviolet phototube needs subsidiary optical filter, and photomultiplier then needs
To work under high voltages, and volume is heavy, efficiency is low, fragile and cost is higher, there is certain office for practical application
It is sex-limited.For silicon detector and photomultiplier, because semi-conducting material has easy to carry, low cost, responsiveness high
The advantages that and receive much concern.
Studying more semi-conducting material at present mainly has the alloy AlGaN of iii-v and the alloy MgZnO of II-VI group.
The GaN reported at present by mix aluminium can band adjust width arrive day-old chick, and be fabricated to MSM (metal-semiconductor-metal) and
The isostructural detectors of p-n.But AlGaN growth temperature is high, and the alloy crystalline quality of high alumina component is poor.ZnO conducts
Another wide bandgap semiconductor, have strong capability of resistance to radiation, high electronics saturation drift velocity, matching single crystalline substrate,
Be readily synthesized, be nontoxic, aboundresources and the advantage such as environment-friendly, be prepare broad stopband ultraviolet detector candidate material it
One.
Most important three parameters are exactly the responsiveness of device, dark current and response time for ultraviolet detector.
Responsiveness and dark current determine the sensitivity of device and the detectivity to weak signal, and responsiveness is the higher the better, and dark current is got over
It is low better.Response time then determines quick discrimination capabilities of the device for signal, in UV warming and ultraviolet communication field pair
Higher in the requirement of response time, the response time, The faster the better.It is necessary to have good for practical ultraviolet detector
Good combination property.This target is realized, in addition to improving the quality of film, post processing and method of modifying to device
It is vital.Current method of modifying, general is difficult to optimize these three important parameters simultaneously.Especially for the sound of device
Between seasonable, it is difficult to further improve, while the reduction with response device degree is likely to.
The content of the invention
In order to solve the above problems, technical solution of the present invention provides a kind of ultraviolet detector and preparation method thereof, improves
The responsiveness of ultraviolet detector, reduces dark current and response time.
To achieve these goals, the present invention provides following technical scheme：
A kind of preparation method of ultraviolet detector, the preparation method include：
One substrate is provided；
Zinc oxide film is formed in the substrate surface；
Fluorine moditied processing is carried out to the surface of the zinc oxide film so that the zinc oxide film has fluorine-containing functional group；
The electrode of preset pattern structure is formed on the surface of the zinc oxide film, the electrode surface has In grains；
Wherein, the functional group is used to increase the adsorbance and the rate of adsorption to oxygen.
Preferably, it is described to include in substrate surface formation zinc oxide film in above-mentioned preparation method：
Pass through molecular beam epitaxial process or MOCVD technique or magnetron sputtering technique shape
Into the zinc oxide film.
Preferably, it is described that zinc oxide film progress fluorine moditied processing is included in above-mentioned preparation method：
The zinc oxide film is immersed in preset time in fluorine-containing solution, to form the functional group；
After being cleaned by deionized water, processing is dried.
Preferably, in above-mentioned preparation method, the preset time is 0.01s-24h；
The concentration of fluorine is 1*10 in the solution-6Mol/L-10mol/L, including endpoint value.
Preferably, in above-mentioned preparation method, the solution is HF solution or KF solution or NaF solution or trifluoro second
Acid solution or trifluoromethanesulfonic acid solution or trifluoroacetic acid solution.
Preferably, in above-mentioned preparation method, the electricity that preset pattern structure is formed on the surface of the zinc oxide film
Pole includes：
Layer gold is formed on the surface of the zinc oxide film；
The layer gold is patterned, forms interdigital electrode；
In grains are set in the interdigital electrode.
Present invention also offers a kind of ultraviolet detector, the ultraviolet detector includes：
Substrate；
Positioned at the zinc oxide film of the substrate surface, fluorine moditied processing, the oxidation are passed through in the surface of the zinc oxide film
Zinc layers have fluorine-containing functional group；
Positioned at the electrode of the preset pattern structure on the zinc oxide film surface, the electrode surface has In grains；
Wherein, the functional group is used to increase the adsorbance and the rate of adsorption to oxygen.
Preferably, in above-mentioned ultraviolet detector, the electrode is gold electrode, thickness 5nm-300nm, including end points
Value.
Preferably, in above-mentioned ultraviolet detector, the electrode is interdigital electrode.
Preferably, in above-mentioned ultraviolet detector, the In grains are the cylindrical structural that diameter is more than 0.5mm.
In ultraviolet detector provided by foregoing description, technical solution of the present invention and preparation method thereof, formed
Before electrode, fluorine moditied processing is carried out to zinc oxide film so that zinc oxide film has fluorine-containing functional group, the fluorine-containing function
Group can increase the adsorbance to oxygen, so as to improve responsiveness, reduce dark current, and the fluorine-containing functional group can increase
To the rate of adsorption of oxygen, so as to reduce the response time.It can be seen that technical solution of the present invention can optimize ultraviolet detector simultaneously
These three characteristics of responsiveness, dark current and response time.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1-Fig. 5 is a kind of schematic flow sheet of the preparation method of ultraviolet detector provided in an embodiment of the present invention；
Fig. 6 is a kind of front and rear I-V curve of zinc oxide ultraviolet detector fluorine modification provided in an embodiment of the present invention；
Fig. 7 is a kind of front and rear photoresponse curve of zinc oxide ultraviolet detector fluorine modification provided in an embodiment of the present invention；
Fig. 8 is a kind of front and rear response time curve of zinc oxide ultraviolet detector fluorine modification provided in an embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
In order to facilitate the understanding of the purposes, features and advantages of the present invention, it is below in conjunction with the accompanying drawings and specific real
Applying mode, the present invention is further detailed explanation.
It is a kind of flow of the preparation method of ultraviolet detector provided in an embodiment of the present invention with reference to figure 1- Fig. 5, Fig. 1-Fig. 5
Schematic diagram, the preparation method include：
Step S11：As shown in Figure 1, there is provided a substrate 1.
Optionally, the substrate is Sapphire Substrate.
Step S12：As shown in Fig. 2 form zinc oxide film 2 on the surface of substrate 1.
It is described to include in substrate surface formation zinc oxide film in the step：By molecular beam epitaxial process (MBE),
Or MOCVD technique (MOCVD) or magnetron sputtering technique form the zinc oxide film.
Step S13：As shown in figure 3, fluorine moditied processing is carried out to the surface of the zinc oxide film 2 so that the zinc oxide
Layer 2 has fluorine-containing functional group.
Wherein, the functional group is used to increase the adsorbance and the rate of adsorption to oxygen.
It is described that zinc oxide film progress fluorine moditied processing is included in the step：First, the zinc oxide film 2 is soaked
The not preset time in fluorine-containing solution, to form the functional group；Then, after being cleaned by deionized water, place is dried
Reason.Specifically, the drying process is to carry out drying processing by nitrogen.
Optionally, the preset time is 0.01s-24h；The concentration of fluorine is 1*10 in the solution-6mol/L-10mol/
L, including endpoint value.The solution is HF solution or KF solution or NaF solution or trifluoroacetic acid solution or trifluoromethanesulfonic acid
Solution or trifluoroacetic acid solution.
Zinc oxide film 2 is after solution soaks preset time, the surface of zinc oxide film 2 and solution reaction, in zinc oxide film 2
Upper surface forms the zinc oxide film 21 of fluorine modification, and the zinc oxide film 21 of fluorine modification has fluorine-containing functional group, by increasing capacitance it is possible to increase right
The adsorbance and the rate of adsorption of oxygen.
Step S14：As shown in Figure 4 and Figure 5, the electrode 3 of preset pattern structure is formed on the surface of the zinc oxide film 2,
The electrode surface has In grains 4.
In the step, the electrode 3 that preset pattern structure is formed on the surface of the zinc oxide film includes：
First, layer gold is formed on the surface of the zinc oxide film.The thickness 5nm-300nm of the layer gold, including endpoint value.
The layer gold can be formed by evaporation process.
Then, the layer gold is patterned, forms interdigital electrode 3.Can be by photoetching and wet-etching technology to described
Layer gold is patterned, and forms the interdigital electrode 3.As shown in figure 5, the interdigital electrode 3 includes two relative electrode lists
Member 30, electrode unit 30 include multiple interdigital 31 and with interdigital 31 ends 32 being connected.Interdigital the 31 of two electrode units 30
It is arranged alternately, and there is gap.In each electrode unit 30, interdigital 31 number is 10-25, including endpoint value.It is two neighboring
Interdigital 31 spacing L1 is 2 μm -10 μm, including endpoint value.Interdigital 31 length L3 is 0.5mm-2mm, including endpoint value.It is interdigital
31 width L2 is 2 μm -10 μm, including endpoint value.
Finally, In grains are set in the interdigital electrode.The In grains 4 are the cylindrical structural that diameter is more than 0.5mm.
The ultraviolet detector that preparation method described in the embodiment of the present invention makes is the zinc oxide ultraviolet detector of MSM structures.
The surface of zinc oxide 2 forms electrode by a metal level.The electrode includes two electrode units 30, two electrode units 30 and oxidation
Zinc layers 2 form MSM structures.
In the preparation method, by carrying out fluorine moditied processing to zinc oxide film 2 so that zinc oxide film 2 has fluorine-containing
Functional group, the fluorine-containing functional group can increase the adsorbance to oxygen, so as to improve responsiveness, reduce dark current, and institute
The rate of adsorption to oxygen can be increased by stating fluorine-containing functional group, so as to reduce the response time.
With reference to specific experimental example, the performance of the ultraviolet detector made to preparation method described in the embodiment of the present invention
Verified.
Zinc oxide film can be formed on a sapphire substrate using molecular beam epitaxial device, then be immersed in zinc oxide film
Concentration is 1*10-510s in mol/L HF solution, then it is washed with deionized water totally, is dried up with dry nitrogen, obtain fluorine and repair
The zinc oxide film of decorations.50nm layer gold is deposited by thermal evaporation again.Layer gold is etched by photoetching and wet-etching technology again, formed
Interdigital electrode, the finger spacing of interdigital electrode is 5 μm, and interdigital number is 10 in each electrode unit of interdigital electrode, interdigital length
Degree is 0.5mm, and interdigital width is 5 μm.Finally, In grains are pressed in interdigital electrode and obtains the ultraviolet spy of zinc oxide of MSM structures
Survey device.The performance of prepared zinc oxide ultraviolet detector is as Figure 6-Figure 8.
As shown in fig. 6, Fig. 6 is a kind of front and rear I-V of zinc oxide ultraviolet detector fluorine modification provided in an embodiment of the present invention
Curve.As shown in Figure 6, when 10V is biased, the dark current of unmodified device is 39nA, the dark current after fluorine is modified
It is reduced to 30nA.
Rung as shown in fig. 7, Fig. 7 is a kind of front and rear light of zinc oxide ultraviolet detector fluorine modification provided in an embodiment of the present invention
Answer curve.As shown in Figure 7, when 10V is biased, the peak response degree of unmodified device is 0.1A/W, after fluorine is modified
Peak response degree be promoted to 0.5A/W.
As shown in figure 8, Fig. 8 is a kind of front and rear response of zinc oxide ultraviolet detector fluorine modification provided in an embodiment of the present invention
Time graph.As shown in Figure 8, when 10V is biased, the response time of unmodified device is 230.9s, after fluorine is modified
Response time be reduced to 13.7s.
In order to detect influence of the reaction time to ultraviolet detector performance, shown by contrast experiment, when zinc oxide film with
When the reaction time of solution is respectively 1s, 5s and 20s, the dark current of prepared zinc oxide ultraviolet detector is respectively
39nA, 38nA, 28nA；Responsiveness is 0.2A/W, 0.3A/W, 0.5A/W respectively；Response time is respectively 200s, 60.9s, 11s.
It is final test result indicates that, in the preparation method, the 10s-20s of the optimum reacting time of zinc oxide film and solution, now,
Zinc oxide ultraviolet detector has preferable dark current, responsiveness and response time.
Preparation method described in the embodiment of the present invention, when preparing zinc oxide ultraviolet detector, fluorine modification is first carried out, it is rear to be formed
Electrode, avoid and carry out caused electrode disengaging problem during fluorine modification after being initially formed electrode.
Tested by photoresponse indicatrix, dark current and the response time to made ultraviolet detector,
Test result surface, preparation method described in the embodiment of the present invention can optimize simultaneously responsiveness, the dark current of ultraviolet detector with
And these three characteristics of response time.Specifically, the photoresponse test system with ultraviolet enhancing xenon lamp and lock-in amplifier can be used
To determine photoresponse indicatrix, the dark current of ultraviolet detector is tested using semiconductor analysis instrument, uses oscillograph and pulse
LASER Light Source tests the response time of ultraviolet detector.
Based on above-mentioned preparation method embodiment, another embodiment of the present invention additionally provides a kind of ultraviolet detector, and this is ultraviolet
Detector is made using above-mentioned preparation method.The structure of the ultraviolet detector is as shown in figure 4 above and Fig. 5.
The ultraviolet detector includes：Substrate 1；Zinc oxide film 2 positioned at the surface of substrate 1, the zinc oxide film 2
Fluorine moditied processing is passed through on surface, and the zinc oxide film 2 has fluorine-containing functional group；Positioned at the default of the surface of zinc oxide film 2
The electrode 3 of graphic structure, the surface of electrode 3 have In grains 4；Wherein, the functional group is used to increase the adsorbance to oxygen
And the rate of adsorption.The surface of zinc oxide film 2 includes the ZnMgO layers 21 of fluorine modification after fluorine moditied processing.
Optionally, the electrode 3 is gold electrode, thickness 5nm-300nm, including endpoint value.The electrode 3 is interdigital electricity
Pole.The In grains 4 are the cylindrical structural that diameter is more than 0.5mm.
Ultraviolet detector described in the embodiment of the present invention has the zinc oxide film of fluorine-containing functional group, the fluorine-containing functional group
The adsorbance to oxygen can be increased, so as to improve responsiveness, reduce dark current, and the fluorine-containing functional group can increase pair
The rate of adsorption of oxygen, so as to reduce the response time.It can be seen that ultraviolet detector described in the embodiment of the present invention can optimize purple simultaneously
These three characteristics of responsiveness, dark current and the response time of external detector.
Each embodiment is described by the way of progressive in this specification, what each embodiment stressed be and other
The difference of embodiment, between each embodiment identical similar portion mutually referring to.For ultraviolet disclosed in embodiment
For detector, due to its with embodiment disclosed in preparation method it is corresponding, so description is fairly simple, related part referring to
Preparation method part illustrates.
The foregoing description of the disclosed embodiments, professional and technical personnel in the field are enable to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (10)
1. a kind of preparation method of ultraviolet detector, it is characterised in that the preparation method includes：
One substrate is provided；
Zinc oxide film is formed in the substrate surface；
Fluorine moditied processing is carried out to the surface of the zinc oxide film so that the zinc oxide film has fluorine-containing functional group；
The electrode of preset pattern structure is formed on the surface of the zinc oxide film, the electrode surface has In grains；
Wherein, the functional group is used to increase the adsorbance and the rate of adsorption to oxygen.
2. preparation method according to claim 1, it is characterised in that described to form zinc oxide film bag in the substrate surface
Include：
Institute is formed by molecular beam epitaxial process or MOCVD technique or magnetron sputtering technique
State zinc oxide film.
3. preparation method according to claim 1, it is characterised in that described that fluorine moditied processing is carried out to the zinc oxide film
Including：
The zinc oxide film is immersed in preset time in fluorine-containing solution, to form the functional group；
After being cleaned by deionized water, processing is dried.
4. preparation method according to claim 3, it is characterised in that the preset time is 0.01s-24h；
The concentration of fluorine is 1*10 in the solution-6Mol/L-10mol/L, including endpoint value.
5. preparation method according to claim 3, it is characterised in that the solution is HF solution or KF solution or NaF
Solution or trifluoroacetic acid solution or trifluoromethanesulfonic acid solution or trifluoroacetic acid solution.
6. preparation method according to claim 1, it is characterised in that it is described formed on the surface of the zinc oxide film it is default
The electrode of graphic structure includes：
Layer gold is formed on the surface of the zinc oxide film；
The layer gold is patterned, forms interdigital electrode；
In grains are set in the interdigital electrode.
7. a kind of ultraviolet detector, it is characterised in that the ultraviolet detector includes：
Substrate；
Positioned at the zinc oxide film of the substrate surface, fluorine moditied processing, the zinc oxide film are passed through in the surface of the zinc oxide film
With fluorine-containing functional group；
Positioned at the electrode of the preset pattern structure on the zinc oxide film surface, the electrode surface has In grains；
Wherein, the functional group is used to increase the adsorbance and the rate of adsorption to oxygen.
8. ultraviolet detector according to claim 7, it is characterised in that the electrode is gold electrode, thickness 5nm-
300nm, including endpoint value.
9. ultraviolet detector according to claim 7, it is characterised in that the electrode is interdigital electrode.
10. ultraviolet detector according to claim 7, it is characterised in that the In grains are the cylinder that diameter is more than 0.5mm
Shape structure.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111816715A (en) * | 2020-08-24 | 2020-10-23 | 中国科学院长春光学精密机械与物理研究所 | Zinc oxide nanowire array ultraviolet detector and preparation method thereof |
| CN111952376A (en) * | 2020-08-24 | 2020-11-17 | 中国科学院长春光学精密机械与物理研究所 | Zinc oxide micrometer ultraviolet detector and preparation method thereof |
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| CN103441186A (en) * | 2013-08-29 | 2013-12-11 | 江苏大学 | Ultraviolet detector manufacturing method |
| CN106784061A (en) * | 2016-12-28 | 2017-05-31 | 中国科学院长春光学精密机械与物理研究所 | A kind of ultraviolet detector and preparation method thereof |
| CN106910786A (en) * | 2017-03-16 | 2017-06-30 | 中国科学院半导体研究所 | A kind of enhanced nano wire of quantum dot and UV photodetector |
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| CN103441186A (en) * | 2013-08-29 | 2013-12-11 | 江苏大学 | Ultraviolet detector manufacturing method |
| CN106784061A (en) * | 2016-12-28 | 2017-05-31 | 中国科学院长春光学精密机械与物理研究所 | A kind of ultraviolet detector and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111816715A (en) * | 2020-08-24 | 2020-10-23 | 中国科学院长春光学精密机械与物理研究所 | Zinc oxide nanowire array ultraviolet detector and preparation method thereof |
| CN111952376A (en) * | 2020-08-24 | 2020-11-17 | 中国科学院长春光学精密机械与物理研究所 | Zinc oxide micrometer ultraviolet detector and preparation method thereof |
| CN111952376B (en) * | 2020-08-24 | 2024-03-08 | 中国科学院长春光学精密机械与物理研究所 | Zinc oxide micro-wire ultraviolet detector and preparation method thereof |
| CN111816715B (en) * | 2020-08-24 | 2024-03-08 | 中国科学院长春光学精密机械与物理研究所 | Zinc oxide nanowire array ultraviolet detector and preparation method thereof |
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