CN110098288B - Oxide thin film device with photodiode effect and preparation method thereof - Google Patents

Oxide thin film device with photodiode effect and preparation method thereof Download PDF

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Publication number
CN110098288B
CN110098288B CN201910267910.9A CN201910267910A CN110098288B CN 110098288 B CN110098288 B CN 110098288B CN 201910267910 A CN201910267910 A CN 201910267910A CN 110098288 B CN110098288 B CN 110098288B
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thin film
substrate
oxide thin
layer
film device
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CN110098288A (en
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刘志钢
唐新桂
唐振华
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Guangdong University of Technology
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Guangdong University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/36—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/36—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
    • H01L33/40—Materials therefor

Abstract

The invention belongs to the technical field of microelectronics, and discloses an oxide thin film device with a photodiode effect and a preparation method thereof, wherein the oxide thin film device comprises a top electrode, an oxide thin film layer, a substrate layer and a bottom electrode; the substrate layer is a p-Si substrate, and the oxide film layer is ZrO2. The invention deposits the oxide film on the substrate by magnetron sputtering method, then plates the metal top electrode on the film and plates the metal bottom electrode on the back of the substrate, forms the metal/oxide film/semiconductor device structure. The device structure is manufactured by annealing in a proper temperature and oxygen atmosphere, and has obvious diode effect.

Description

Oxide thin film device with photodiode effect and preparation method thereof
Technical Field
The invention belongs to the technical field of microelectronics, and particularly relates to an oxide thin film device with a photodiode effect and a preparation method thereof.
Background
In recent years, with the continuous development of technology, thin film devices are receiving increasing attention, and have been developed in various fields, and photodiodes are one of the promising directions. A photodiode is a light detector that can convert light into a voltage or current.
Photodiodes are substantially similar to conventional semiconductor diodes except that they may be exposed directly near the light source or through a small transparent window, fiber optic package, to allow light to reach the light sensitive region of the device to detect the optical signal. The basic structure of a photodiode is very simple and is usually formed by a PN junction. When a photon of sufficient energy strikes the photosensitive region of the device, it will emit an electron, thereby generating a free electron, accompanied by a positively charged hole, a mechanism known as the internal photoelectric effect. If the absorption of photons occurs in the depletion layer of the PN junction, the internal power plants in the region will remove the barrier between them, allowing holes to move towards the anode and electrons to move towards the cathode, so that a photocurrent is generated.
PN junction photodiodes, like other types of photodetectors, have not found widespread use in devices such as photoresistors, photocouplers, and photomultiplier tubes. They are capable of outputting corresponding current-voltage signals according to the intensity of the received light. In research and industrial production, photodiodes are often used to accurately measure light intensity to meet the requirements of some special situations.
Disclosure of Invention
To overcome the above-mentioned shortcomings and drawbacks of the prior art, it is a primary object of the present invention to provide an oxide thin film device with photodiode effect.
Another objective of the present invention is to provide a method for manufacturing the above oxide thin film device with photodiode effect.
The purpose of the invention is realized by the following technical scheme:
an oxide thin film device having a photodiode effect, the oxide thin film device comprising a top electrode, an oxide thin film layer, a substrate layer, and a bottom electrode; the substrate layer is a p-Si substrate, and the oxide film layer is ZrO2。
Preferably, the thickness of the oxide thin film layer is 40-50 nm.
Preferably, the top electrode is one or more of Au, Ti, Al, Ag, W, TiN, or Pt.
Preferably, the bottom electrode is W, Cu, Al, TiN or Pt.
The preparation method of the oxide thin film device with the photodiode effect comprises the following specific steps:
s1, wiping the surfaces of a Zr target and a W target by using abrasive paper, removing impurities on the surfaces, then cleaning the targets by using absolute ethyl alcohol, and cleaning;
s2, soaking the p-Si substrate in HF solution to remove SiO generated on the surface of the substrate2；
S3, installing the target and the substrate, opening circulating water, starting a main power switch, starting a mechanical pump, and regulating and controlling an air valve to reduce the pressure to below 10 Pa; after the pressure is stable, the molecular pump is started, and the plate valve is regulated and controlled to reduce the pressure to 5 multiplied by 10-3Pa below; closing the plate valve and introducing O2Ar, adjusting a valve, simultaneously micro-adjusting a plate valve, keeping the vacuum at 4.5-5.9 Pa, starting a radio frequency power supply, and preheating a filament;
s4, preparing to start up, adjusting power, controlling current to be 280-320 mA and voltage to be 0.6-0.8 kV, and sputtering to obtain an oxide film;
s5, annealing the oxide film at 600-650 ℃ under the oxygen condition, putting the substrate on which the oxide film is deposited after annealing in a measurement and control sputtering instrument again, repeating the steps S1-S4, plating a layer of metal W on the back surface of the substrate on which the oxide film is deposited in the atmosphere of only Ar, and plating a layer of metal Au point electrode on the front surface of the substrate, thus obtaining the oxide film device with the photodiode effect.
Preferably, the substrate layer in step S3 is a p-Si substrate
Preferably, in step S3, the Ar: o is2The flow ratio of (2) is 8: (2-3).
Preferably, the preheating time in the step S3 is 3-5 min.
Preferably, the sputtering time in the step S4 is 30-40 min.
Preferably, the annealing time in the step S5 is 10-15 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention deposits the oxide film on the substrate by magnetron sputtering method, then plates the metal top electrode on the film and plates the metal bottom electrode on the back of the substrate, forms the metal/oxide film/semiconductor device structure. The device structure is manufactured by annealing in a proper temperature and oxygen atmosphere, and has obvious diode effect.
2. The oxide thin film device with the diode effect has the advantages of sensitive response, good linear change, high photoelectric conversion efficiency, strong anti-interference capability, small volume and long service life.
3. The invention has simple preparation process, good and stable diode effect and wide application prospect in the field of light intensity detectors.
Drawings
FIG. 1 shows the ZrO plating on a p-Si substrate according to the present invention2A thin film device structure diagram and a test sketch thereof;
FIG. 2 shows ZrO in example 12Applying an I-V curve chart of a +/-1V voltage test to the thin film device under a dark condition;
FIG. 3 shows ZrO in example 12Under the condition that only ultraviolet light is added to the thin film device, the I-V curve chart of the light intensity test is continuously increased;
FIG. 4 shows ZrO in example 12The intensity of ultraviolet light of the thin film device is 20.30mW/cm2I-T curve of the voltage test of plus or minus 1V is applied under the condition.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Preparation of ZrO by magnetron sputtering coating method2Thin-film device: preparing Zr and W targets and p-Si, wiping the surface of the metal target by using abrasive paper, and then cleaning the metal target by using absolute ethyl alcohol. Wiping the surface of the Si wafer with dilute HF solution to remove SiO on the surface2。
2. Installing and fixing the cleaned substrate and the target material according to the experimental steps, and sputtering ZrO according to the experimental steps2Film, ZrO2The thickness of the thin film layer was 40 nm.
3. The sputtered ZrO2The film is placed in a rapid annealing furnace for annealing at 600 ℃ for 10 min. Then will beThe annealed sample is coated with a metal Au point electrode on the film by a small vacuum coating machine, and a metal W bottom electrode on the back of the substrate to prepare ZrO with photodiode effect2A thin film device.
FIG. 1 is a simplified diagram of the structure of a device and its testing. The oxide thin film device comprises a substrate layer p-Si substrate and an oxide thin film layer ZrO2And an electrode layer, wherein the electrode layer comprises a top electrode and a bottom electrode. The device is simple to prepare, and only a layer of ZrO needs to be sputtered on the cleaned substrate2The film is plated with metal point electrode and the back of the substrate is plated with metal bottom electrode to form the basic MOS structure device. FIG. 2 shows the I-V curve measured by applying + -1V voltage to the device under dark conditions. It can be seen from fig. 2 that the device is in the off state when a negative voltage is applied; the current at which the device conducts when a forward voltage is applied is also of the nanoamp level. FIG. 3 is an I-V curve measured by applying + -1V voltage under the condition of UV irradiation while increasing the irradiation intensity. As can be seen from fig. 3, as the intensity of the ultraviolet light is increased, the negative conduction condition is increased, and the positive change is not obvious and remains substantially unchanged. FIG. 4 shows the ultraviolet light intensity of 20.30mW/cm in this example2Under the condition, when a voltage of-1V is applied, an I-T curve graph is measured. The time interval between the presence and absence of light is 100s, and the sensitivity of the device to light is relatively stable from the view point of the current variation in fig. 4.
Example 2
1. Preparation of ZrO by magnetron sputtering coating method2Thin-film device: preparing Zr and W targets and p-Si, wiping the surface of the metal target by using abrasive paper, and then cleaning the metal target by using absolute ethyl alcohol. Wiping the surface of the Si wafer with dilute HF solution to remove SiO on the surface2。
2. Installing and fixing the cleaned substrate and the target material according to the experimental steps, and sputtering ZrO according to the experimental steps2Film, ZrO2The thickness of the thin film layer was 50 nm.
3. The sputtered ZrO2Film is put in rapid annealingAnnealing at 650 deg.C for 10 min. Then, the annealed sample is coated with a metal Au point electrode on the film by a small-sized vacuum coating machine, and a metal W bottom electrode is coated on the back of the substrate to prepare the ZrO with the photodiode effect2A thin film device.
Example 3
1. Preparation of ZrO by magnetron sputtering coating method2Thin-film device: preparing Zr and W targets and p-Si, wiping the surface of the metal target by using abrasive paper, and then cleaning the metal target by using absolute ethyl alcohol. Wiping the surface of the Si wafer with dilute HF solution to remove SiO on the surface2。
2. Installing and fixing the cleaned substrate and the target material according to the experimental steps, and sputtering ZrO according to the experimental steps2Film, ZrO2The thickness of the thin film layer was 45 nm.
3. The sputtered ZrO2The film is placed in a rapid annealing furnace for annealing for 15min at the temperature of 600 ℃. Then, the annealed sample is coated with a metal Au point electrode on the film by a small-sized vacuum coating machine, and a metal W bottom electrode is coated on the back of the substrate to prepare the ZrO with the photodiode effect2A thin film device.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (4)

1. An oxide thin film device having a photodiode effect, the oxide thin film device comprising a top electrode, an oxide thin film layer, a substrate layer and a bottom electrode; the substrate layer is a p-Si substrate, and the oxide film layer is ZrO2(ii) a The top electrode is more than one of Au, Ti, Al, Ag, W, TiN or Pt; the bottom electrode is W, Cu, Al, TiN or Pt; the thickness of the oxide thin film layer is 40-50 nm;
the preparation method of the oxide thin film device with the photodiode effect comprises the following specific steps:
s1, wiping the surfaces of a Zr target and a W target by using abrasive paper, removing impurities on the surfaces, then cleaning the targets by using absolute ethyl alcohol, and cleaning; wiping the surface of the Si wafer with dilute HF solution to remove SiO on the surface2；
S2, installing a target material and a substrate, opening circulating water, starting a main power switch, starting a mechanical pump, and regulating and controlling an air valve to reduce the pressure to below 10 Pa; after the pressure is stable, the molecular pump is started, and the plate valve is regulated and controlled to reduce the pressure to 5 multiplied by 10-3Pa below; closing the plate valve and introducing O2And Ar, said Ar: o is2The flow ratio of (2) is 8: (2-3); adjusting a valve, simultaneously micro-adjusting a plate valve, keeping the vacuum at 4.5-5.9 Pa, starting a radio frequency power supply, and preheating a filament;
s3, preparing to start up, adjusting power, controlling current to be 280-320 mA and voltage to be 0.6-0.8 kV, and sputtering;
s4, annealing the oxide film at 600-650 ℃ under the oxygen condition; and putting the substrate on which the oxide film is deposited after annealing in a magnetron sputtering instrument again, plating a layer of bottom electrode on the back surface of the substrate on which the oxide film is deposited under the atmosphere of only Ar, and plating a layer of top electrode on the front surface of the substrate, thus obtaining the oxide film device with the photodiode effect.
2. The oxide thin film device with photodiode effect as claimed in claim 1, wherein the preheating time in step S2 is 3-5 min.
3. The oxide thin film device having a photodiode effect according to claim 1, wherein the sputtering time in step S3 is 30-40 min.
4. The oxide thin film device with photodiode effect of claim 1, wherein the annealing time in step S4 is 10-15 min.
CN201910267910.9A 2019-04-03 2019-04-03 Oxide thin film device with photodiode effect and preparation method thereof Expired - Fee Related CN110098288B (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
US4403239A (en) * 1979-12-26 1983-09-06 Shunpei Yamazaki MIS Type semiconductor photoelectric conversion device
CN101667611A (en) * 2009-09-15 2010-03-10 上海交通大学 Preparation method of solar micro battery on basis of directional carbon nano tube
US7833904B2 (en) * 2005-06-16 2010-11-16 The Trustees Of Columbia University In The City Of New York Methods for fabricating nanoscale electrodes and uses thereof

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US4403239A (en) * 1979-12-26 1983-09-06 Shunpei Yamazaki MIS Type semiconductor photoelectric conversion device
US7833904B2 (en) * 2005-06-16 2010-11-16 The Trustees Of Columbia University In The City Of New York Methods for fabricating nanoscale electrodes and uses thereof
CN101667611A (en) * 2009-09-15 2010-03-10 上海交通大学 Preparation method of solar micro battery on basis of directional carbon nano tube

Non-Patent Citations (3)

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Title
Atomic and electronic structures of amorphous ZrO2 and HfO2 films;Vladimir Gritsenko et al.;《Microelectronic Engineering》;20050407;第81卷;第524-529页 *
Effect of Annealing Temperature on Structural and Electrical Properties of Al/ZrO2/p-Si MIS Schottky Diodes;K. Sasikumar et al.;《Silicon》;20180629;第11卷;第137-143页 *
Vladimir Gritsenko et al..Atomic and electronic structures of amorphous ZrO2 and HfO2 films.《Microelectronic Engineering》.2005,第81卷第524-529页. *

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