CN101562208A - Back incident-type TiO* UV detector and preparation method thereof - Google Patents
Back incident-type TiO* UV detector and preparation method thereof Download PDFInfo
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- CN101562208A CN101562208A CNA2009100670322A CN200910067032A CN101562208A CN 101562208 A CN101562208 A CN 101562208A CN A2009100670322 A CNA2009100670322 A CN A2009100670322A CN 200910067032 A CN200910067032 A CN 200910067032A CN 101562208 A CN101562208 A CN 101562208A
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Abstract
The invention belongs to the field of semiconductor optoelectronic detectors, in particular relates to a back incident-type UV detector with quartz as a substrate, nano-TiO2 thin film as a basic UV detection material and Ni as a metal electrode, and a preparation method thereof. The detector takes the quartz as the substrate and adopts an M-S-M (metal-semiconductor-metal) structure. The method for manufacturing the UV detector comprises the steps of adopting a sol-gel technique to grow a TiO2 nanometer thin film on the quartz substrate, evaporating a layer of thin Ni on the prepared TiO2 thin film by a magnetron sputtering method to achieve electrode contact, and adopting lithography technology to obtain Ni inserted-finger shape electrodes. The UV detector in an MSM planar double schottky barrier structure adopts a back incident-type working mode and can greatly improve responsiveness. The detector has good detection performance for the UV rays 250 to 350 nm in wavelength.
Description
Technical field
The invention belongs to semiconductor photo detector spare field, being specifically related to a kind of is substrate with the quartz, with nano-TiO
2Film is basic ultraviolet detector material, is back incident-type ultraviolet light detector of metal electrode and preparation method thereof with Ni.
Background technology
It is strong and be applicable to adverse circumstances good characteristics such as (as hot environments) that ultraviolet light detector has an antijamming capability, has significant application value at scientific research, military affairs, space flight, environmental protection, fire prevention and many industrial control fields.
Traditional ultraviolet light detector is mainly based on silica-based ultraviolet light fulgurite and photomultiplier etc., though they are highly sensitive, shortcomings such as but existence needs additive filter or volume is big, fragile, need work under high voltage are difficult to satisfy the needs that modern electronic technology develops.In recent years, very swift and violent based on the ultraviolet warning and the tracking technique development of guided missile ultraviolet detection, and to the higher requirement of ultraviolet detector device proposition.Therefore efficient height, cost low, be easy to integrated, be suitable for the novel wide bandgap semiconductor ultraviolet light detector of under adverse circumstances, working and large scale ultraviolet imagery device and become the focus that photodetection field is in the world paid close attention to.
The semiconductor material with wide forbidden band that is used for ultraviolet light detector at present is a lot, mainly comprises SiC, ZnO and GaN class III-V compounds of group etc.But, up to now, but do not have a kind of wide bandgap semiconductor ultraviolet light detector and image device can become the main product in this field.Wherein chief reason is to lack backing material and the effective technical means for preparing LSI device.In addition, with these material preparation ultraviolet light detectors, not only preparation technology's difficulty Ben Shen is big, and to the requirement harshness of equipment and processing conditions, cost is high too.
Because wide bandgap semiconductor TiO
2Material price is cheap, itself have extraordinary weatherability, physics and chemical stability, suitable photoelectric characteristic, and the means of numerous maturations are arranged aspect material preparation, to satisfy needs of different applications, therefore aspect ultraviolet detector, demonstrate unique application prospect.
Summary of the invention
The object of the invention provides a kind of with TiO
2Nano-crystal film is the back incident-type ultraviolet light detector of the two Schottky barrier structures in the metal-semiconductor-metal plane of matrix and the preparation method of this detector.
TiO
2As a kind of oxide semiconductor material, energy gap is bigger, is 3.0～3.2ev, and visible light is absorbed hardly, and the ultraviolet ray below the 350nm is had good absorption characteristic, is the ideal material of preparation ultraviolet light detector.The present invention makes metal-TiO with device
2-metal flat structure is utilized TiO
2Have the characteristic that select to absorb ultraviolet light, the photon of its absorption is converted into the signal of telecommunication, thereby reaches the purpose that ultraviolet ray is surveyed.This device is made up of two back-to-back Schottky barriers, and there always have a potential barrier to be in during work to be partially anti-, so the dark current of device is little, have characteristics such as high sensitivity, high-responsivity, and device architecture is simple, cost is low, it is integrated to be easy to.
The present invention adopts quartzy as substrate, with TiO
2Prepare the new ultra-violet photo-detector as basis material, broken away from the predicament of the shortage of wide bandgap semiconductor ultraviolet light detector for a long time suitable substrate, for large tracts of land, array ultraviolet light detector and ultraviolet imagery systematic research lay the foundation.The technology that the present invention simultaneously adopts simple and with the semiconductor planar process compatible, be easy to integratedly, be suitable for producing in enormous quantities, thereby have important use and be worth.
The present invention adopts the quartzy substrate that is, therefore device can be made back of the body incident mode of operation, thereby the effective working region that increases device makes device sensitivity bring up to 500A/W.Simultaneously because the TiO of conventional method preparation
2Be n type material, adopt back of the body incident structure, can not cause the slow problem of response speed that produces owing to hole mobility is low.
Detector involved in the present invention is characterized in that: comprise quartz substrate, the nanocrystalline TiO that adopts sol-gal process to grow on quartz substrate from top to bottom successively
2Film, at nanocrystalline TiO
2Ni with the magnetron sputtering method preparation on the film inserts the finger electrode.Ultraviolet light to be detected is from quartz substrate incident.TiO
2Film thickness is 0.10～0.20 μ m, and it is 0.04～0.1 μ m that metal Ni inserts the thickness that refers to electrode, inserts to refer to that electrode width is 5～30 μ m, inserts to refer to that electrode spacing is 10～60 μ m.
MSM planar structure back incident-type TiO of the present invention
2The preparation process of ultraviolet light detector is as follows:
(1) processing of substrate
Quartz substrate is placed acetone, ethanol and deionized water successively, and ultrasonic cleaning is 5～10 minutes respectively, 100～120 ℃ of following dry for standby;
(2) nanocrystal TiO
2The preparation of film
Adopt the sol-gel technique TiO that on the quartz substrate of cleaning, grows
2Nano thin-film: under 15～25 ℃ of temperature conditions, 5～20mL butyl titanate is added drop-wise in 50～200mL absolute ethyl alcohol under 500～1000 rev/mins of stirrings, be added dropwise to 5～20mL glacial acetic acid again,, obtain the yellow solution of homogeneous transparent through 30～90 minutes stirring;
The speed of 5～20mL deionized water with 0.5～2mL/min slowly is added drop-wise in the above-mentioned solution again, continue stirred 1～2 hour, obtain the faint yellow colloidal sol of homogeneous transparent, it is stand-by that it is placed ageing 2～6 hours;
The method that adopts spin coating is spin-coated on the colloidal sol of ageing and forms film on the quartz substrate, and spin speed is 1000～3000 rev/mins; At last film is put into the Muffle furnace sintering together with substrate, 400～800 ℃ of temperature, the time is 1～4 hour, powered-down is cooled to room temperature afterwards, repeats spin coating and sintering process 3～5 times, promptly obtains required TiO on quartz substrate
2Film, film thickness are 0.10～0.20 μ m.
(3) photoresist is inserted the preparation that refers to structure
The nanocrystalline TiO that is preparing
2Adopt standard photolithography process preparation and the photoresist of inserting the complementation of finger electrode structure to insert on the film and refer to that structure, photoresist covering place finally become no metal and insert the zone that refers to electrode.
Concrete grammar is at TiO
2Spin coating one layer thickness is the photoresist (BP212, eurymeric approaches glue, 2500～3500 rev/mins of rotating speeds) of 1～2 μ m on the film, under 70～90 ℃ of conditions before the baking 10～30 minutes; The mask plate exposed photoresist of the slotting finger of employing and metal electrode structure complementation 40～50 seconds, (developer solution was made into by 1: 1 by above-mentioned eurymeric photoresist developing liquid and deionized water, exposes TiO after the development through 10～20 seconds developments
2Film, its shape and position are the metal of need making and insert shape and the position that refers to electrode), at last 110～130 ℃ of following post bakes 20～30 minutes, obtain needed photoresist and insert and refer to structure, it is 10～60 μ m that photoresist is inserted the width that refers to structure, and it is 5～30 μ m that photoresist is inserted the spacing that refers to structure;
(4) adopt magnetron sputtering technique to prepare metal Ni and insert the finger electrode
Having photoresist to insert the substrate that refers to structure on the surface places magnetron sputtering vacuum chamber, is evacuated to 2.0 * 10
-3～4.0 * 10
-3Pa; Logical then Ar gas is regulated air pressure to 0.4～1.2Pa, and sputtering power is 50～100W, sputter 20～40 minutes, and the electrode material of sputter is Ni; It is 5～30 μ m that the metal that obtains is inserted the width that refers to electrode, and it is 10～60 μ m that metal is inserted the spacing that refers to electrode; It is 0.04～0.1 μ m that metal is inserted the thickness that refers to electrode.Place acetone ultrasonic substrate at last, photoresist that is not exposed and the Ni that covers on it are stripped from, and with drying up behind the deionized water rinsing, obtain MSM planar structure back incident-type TiO
2Ultraviolet light detector.
Description of drawings
Fig. 1: device architecture figure of the present invention;
Fig. 2: the dark current characteristic of the prepared device of the present invention;
Fig. 3: the response characteristics to light curve of the prepared device of the present invention under the 5V bias voltage.
As shown in Figure 1, ultraviolet light sees through quartz substrate from the device back surface incident, impinges upon TiO2On, produce Photoelectric current; Each component names is: quartz substrate 1, TiO2Film 2, Ni insert and refer to electrode 3, incident uv 4.
As shown in Figure 2, the dark current of device illustrates that in the nA magnitude dark current characteristic of device is good as can be known;
As shown in Figure 3, from 450nm to 350nm, the photoresponse curve basic horizontal of device. Work as optical wavelength In the time of near the arrival 350nm, an obvious ABSORPTION EDGE is arranged, illustrate that device of the present invention has well at ultraviolet band Response, can be as surveying ultraviolet ray.
Embodiment
At first adopt sol-gel technique, growth thickness is the TiO of 0.15 μ m on the quartz substrate of cleaning
2Nano thin-film.Concrete grammar is under the normal temperature 10mL butyl titanate to be added drop-wise in the 100mL absolute ethyl alcohol under 1000 rev/mins of stirrings, is added dropwise to the 10mL glacial acetic acid again, through 60 minutes stirring, obtains the yellow solution of homogeneous transparent; Again the speed of 10mL deionized water with 1mL/min slowly is added drop-wise in the above-mentioned solution, continues to stir 2 hours, obtain the faint yellow colloidal sol of homogeneous transparent, it is placed ageing 5 hours.The method of employing spin coating is spin-coated on the colloidal sol of ageing on the quartz substrate, and spin speed is 2500 rev/mins; Then film is put into Muffle furnace sintering 2h, sintering temperature is 600 ℃, obtains TiO
2Film.The thickness of film is about 150nm.
The TiO that is preparing
2On the film, the photoresist that adopts standard photolithography process preparation and metal to insert the complementation of finger electrode structure is inserted and is referred to that structure, photoresist covering place will become no metal and insert the zone that refers to electrode.It is 40 μ m that photoresist is inserted the slotting finger widths that refers to structure, and photoresist is inserted the slotting finger spacing that refers to structure and is 20 μ m, and is corresponding, and it is 20 μ m that metal is inserted the width that refers to electrode, and it is 40 μ m that metal is inserted the spacing that refers to electrode.
Adopt magnetron sputtering technique to insert and refer to sputter layer of Ni on the structure at photoresist.Base vacuum degree 3.0 * 10 in the operation
-3Pascal, sputter gas is an Ar gas, air pressure 0.8 Pascal, sputtering power is 80 watts, sputtering time 30 minutes.The thickness of the Ni electrode that finally obtains is 0.05 μ m.After the sonicated, photoresist and the Ni that covers on it are stripped from, and promptly obtain the device that this patent is invented in acetone.Its structure as shown in Figure 1.
After the element manufacturing, the photoelectric characteristic of device is tested.The dark current of measuring element in the darkroom, as Fig. 2, the dark current of device is in the nA magnitude as can be known.With device of the present invention and resistance is that the resistance R of 5.1M is connected, with the deuterium lamp of 30W be light source irradiation on device of the present invention, measuring resistance R both end voltage, the electric current of the device that obtains indirectly flowing through.Use monochromator, continuously change the optical wavelength that is radiated on the device, be one with 5nm and measure, in 450nm arrives the 250nm scope, the photoresponse of measuring element, the device applying bias is 5V, obtains photoresponse curve, as Fig. 3.As seen from the figure, from 450nm to 350nm, the photoresponse curve basic horizontal, this moment, device was to not response of light.In the time of near optical wavelength arrives 350nm, a tangible ABSORPTION EDGE is arranged, and along with wavelength reduces, responsiveness increases gradually, illustrates that the present invention has good response at ultraviolet band, can be as surveying ultraviolet ray.
Claims (5)
1, back incident-type TiO
2Ultraviolet light detector is characterized in that: comprise quartz substrate (1) from top to bottom successively, adopt sol-gal process to go up the nanocrystalline TiO of growth in quartz substrate (1)
2Film (2), at nanocrystalline TiO
2Ni with the magnetron sputtering method preparation on the film inserts finger electrode (3), and ultraviolet light to be detected (4) is from quartz substrate (1) incident.
2, back incident-type TiO as claimed in claim 1
2Ultraviolet light detector is characterized in that: TiO
2Film (2) thickness is 0.10～0.20 μ m, and it is 0.04～0.1 μ m that metal Ni inserts the thickness that refers to electrode (3), inserts to refer to that electrode width is 5～30 μ m, inserts to refer to that electrode spacing is 10～60 μ m.
3, back incident-type TiO
2The preparation method of ultraviolet light detector, its step is as follows:
A, quartz substrate is placed acetone, ethanol and deionized water successively, ultrasonic cleaning is 5～10 minutes respectively, 100～120 ℃ of following dry for standby;
B, adopt the sol-gel technique TiO that on the quartz substrate of cleaning, grows
2Nano thin-film;
C, the nanocrystalline TiO that is preparing
2Adopt standard photolithography process preparation and the photoresist of inserting the complementation of finger electrode structure to insert on the film and refer to that structure, photoresist covering place finally become no metal and insert the zone that refers to electrode;
D, the substrate that has photoresist to insert the finger structure on the surface place magnetron sputtering vacuum chamber, are evacuated to 2.0 * 10
-3～4.0 * 10
-3Pa; Logical then Ar gas is regulated air pressure to 0.4～1.2Pa, and sputtering power is 50～100W, sputter 20～40 minutes, and the electrode material of sputter is Ni; Place acetone ultrasonic substrate at last, photoresist that is not exposed and the Ni that covers on it are stripped from, and with drying up behind the deionized water rinsing, are comprised quartz substrate (1), nanocrystalline TiO at last successively
2Film (2), Ni insert the MSM planar structure back incident-type TiO that refers to electrode (3)
2Ultraviolet light detector.
4, back incident-type TiO as claimed in claim 3
2The preparation method of ultraviolet light detector is characterized in that: adopt the sol-gel technique TiO that grows on the quartz substrate of cleaning
2Nano thin-film, it at first is under 15～25 ℃ of temperature conditions, and 5～20mL butyl titanate is added drop-wise in 50～200mL absolute ethyl alcohol under 500～1000 rev/mins of stirrings, is added dropwise to 5～20mL glacial acetic acid again, through 30～90 minutes stirring, obtain the yellow solution of homogeneous transparent;
And then the speed of 5～20mL deionized water with 0.5～2mL/min slowly is added drop-wise in the above-mentioned solution, continue to stir 1～2 hour, obtain the faint yellow colloidal sol of homogeneous transparent, it is stand-by that it is placed ageing 2～6 hours;
The method that adopts spin coating at last is spin-coated on the colloidal sol of ageing and forms film on the quartz substrate, and spin speed is 1000～3000 rev/mins; At last film is put into the Muffle furnace sintering together with substrate, 400～800 ℃ of temperature, the time is 1～4 hour, powered-down is cooled to room temperature afterwards, repeats spin coating and sintering process 3～5 times, promptly obtains required TiO on quartz substrate
2Film, film thickness are 0.10～0.20 μ m.
5, back incident-type TiO as claimed in claim 3
2The preparation method of ultraviolet light detector is characterized in that: the nanocrystalline TiO that is preparing
2Adopt the standard photolithography process preparation to insert with the photoresist of inserting the complementation of finger electrode structure on the film and refer to structure, its method is at TiO
2Spin coating one layer thickness is the photoresist of 1～2 μ m on the film, under 70～90 ℃ of conditions before the baking 10～30 minutes; The mask plate exposed photoresist of the slotting finger of employing and metal electrode structure complementation 40～50 seconds, development through 10～20 seconds, at last 110～130 ℃ of following post bakes 20～30 minutes, obtain needed photoresist and insert the finger structure, it is 10～60 μ m that photoresist is inserted the width that refers to structure, and it is 5～30 μ m that photoresist is inserted the spacing that refers to structure.
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