CN110735114A - composition for semiconductor sensor based on zinc oxide doping - Google Patents
composition for semiconductor sensor based on zinc oxide doping Download PDFInfo
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- CN110735114A CN110735114A CN201910937329.3A CN201910937329A CN110735114A CN 110735114 A CN110735114 A CN 110735114A CN 201910937329 A CN201910937329 A CN 201910937329A CN 110735114 A CN110735114 A CN 110735114A
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- metal
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- zinc oxide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
Abstract
The invention discloses compositions for a semiconductor sensor doped based on zinc oxide, which comprise more than 99 wt% of a zinc part, a mixed metal element dopant part and a second metal element dopant part, wherein the mixed metal dopant part and the second metal dopant part are present in a weight ratio of 0.5-1:2-2.5, the mixed metal dopant part has a bond length produced by metal elements and oxygen elements in a zinc oxide unit cell smaller than that of the zinc elements and oxygen elements, and the second metal dopant part has a bond length produced by metal elements and oxygen elements in the zinc oxide unit cell larger than that of the zinc elements and oxygen elements.
Description
Technical Field
The invention relates to semiconductor sensor compositions based on zinc oxide doping.
Background
The semiconductor-oxide sensor analyzes the gas concentration by the change of the resistance value, and the alcohol tester is actually composed of an alcohol sensor (corresponding to a rheostat that varies with the alcohol concentration) and constant resistors and voltmeters or ammeters.
The existing zinc oxide doped with vanadium pentoxide and lanthanum oxide has low oxygen adsorption effect due to rapid expansion of unit cell volume of the zinc oxide, and the invention aims to prepare compositions for the semiconductor sensor doped with zinc oxide.
Disclosure of Invention
The present invention has an object to provide zinc oxide-doped semiconductor sensor compositions for solving the above problems.
In order to achieve the above objects, the present invention is achieved by a technical solution of kinds of zinc oxide-doped-based composition for a semiconductor sensor, the composition comprising more than 99 wt% of a zinc part, a mixed metal element dopant part, and a second metal element dopant part;
said th mixed metal dopant portion and said second metal dopant portion being present in a weight ratio of 0.5-1: 2-2.5;
the mixed metal dopant moiety has a chemical bond length in the zinc oxide unit cell produced by the metal element and oxygen element that is less than the bond length of the zinc element and oxygen element;
the second metal dopant part has a chemical bond length produced by metal elements and oxygen elements in the zinc oxide unit cell larger than the bond length of the zinc elements and the oxygen elements;
the th mixed metal dopant part comprises vanadium pentoxide and lanthanum oxide;
the mixed-metal dopant moiety further includes groups of metal elements that increase the unit cell volume of zinc oxide when doped;
the mixed metal dopant is doped by a pulse laser deposition method, the pulse laser deposition method comprises the following steps of mixing and ball-milling metals in mixed metal dopant and zinc with the purity of more than 99% according to a proportion for 24 hours, presintering at 600-700 ℃ for 4-8 hours, pressing under the pressure of 20-30MPa into a wafer with the diameter of 30-50mm and the thickness of 3mm, and sintering at 1000-1200 ℃ for 4-8 hours to obtain a metal zinc target material, wherein the substrate is a silicon single crystal, the metal zinc target material is arranged in a pulse laser deposition rotating target position, the substrate is fixed on a self-rotating sample holder, the distance between a buffer gas substrate with argon and oxygen and the metal zinc target is 20mm, the substrate temperature is 380-550 ℃, the laser power density is 1-3, the laser pulse width is 25ns, the frequency is 1-50 Hz, and the power is 30-300W to obtain mixed metal-doped zinc oxide;
the second metal element dopant is partially doped by a radio frequency reactive sputtering method, wherein the radio frequency reactive sputtering method comprises the following steps of under the sputtering condition that the pre-vacuum before sputtering is 5-6 Pa, the substrate is th mixed metal doped zinc oxide obtained by a pulse laser deposition method, the sputtering target is a metal zinc target with the diameter of 10mm and the purity of more than 99.99%, the sputtering reaction gas is mixed gas of argon and oxygen, the distance between the substrate and the metal zinc target is 50mm, the substrate temperature is 100-300 ℃, the sputtering power is 60-200W, the sputtering pressure is 1-3.8 Pa, and the sputtering time is 1-2 h.
In particular, the mixed metal dopant includes a group of tantalum or calcium elements that increase the unit cell volume of zinc oxide.
In particular, the second metal dopant is indium element.
The invention has the beneficial effects that: the composition for the semiconductor sensor based on the zinc oxide doping utilizes the sensitivity of the zinc oxide doped with vanadium pentoxide and lanthanum oxide to alcohol to manufacture the semiconductor sensor, and simultaneously reduces the expansion of the unit cell volume of the zinc oxide based on the principle of the semiconductor sensor and increases the adsorption effect of the composition to oxygen.
Detailed Description
Specific example 1: a composition for a semiconductor sensor doped based on zinc oxide, the composition comprising more than 99 wt% of a zinc portion, a th mixed metal element dopant portion and a second metal element dopant portion, the th mixed metal dopant portion and the second metal dopant portion being present in a weight ratio of 0.5:2, the th mixed metal dopant portion comprising vanadium, lanthanum and calcium, the th mixed metal dopant being doped by a pulsed laser deposition method, the pulsed laser deposition method comprising the steps of mixing vanadium, lanthanum and calcium with a metal zinc having a purity of more than 99% in a ratio, ball milling for 24 hours at 600-700 ℃ for pre-burning for 4-8 hours, pressing into a wafer having a diameter of 30-50mm and a thickness of 3mm under a pressure of 20-30MPa, sintering for 4-8 hours at 1000-1200 ℃ to obtain a metal zinc target, the substrate being a silicon single crystal, loading the metal zinc target into a pulsed laser deposition rotary target, the substrate being fixed on a rotatable support, introducing a buffer gas of argon and oxygen, and sintering the metal target at a temperature of 1000-1200 ℃ for 4-8 hours to obtain a substrate doped with a laser power of a laser doping frequency of 380-300 Hz, and a laser doping frequency of 3625 Hz for a substrate of 1-300 Hz;
the indium element is doped by a radio frequency reactive sputtering method, wherein the radio frequency reactive sputtering method comprises the following steps of pre-vacuum of 5-6 Pa before sputtering, a substrate of th mixed metal-doped zinc oxide obtained by a pulse laser deposition method, a metal zinc target with the diameter of 10mm and the purity of more than 99.99 percent, a sputtering reaction gas of mixed gas of argon and oxygen, a distance between the substrate and the metal zinc target of 50mm, the substrate temperature of 100 ℃ and 300 ℃, the sputtering power of 60-200W, the sputtering pressure of 1-3.8 Pa and the sputtering time of 1-2 h.
Specific example 2:
composition for semiconductor sensor doped based on zinc oxide, the composition comprises more than 99 wt% of zinc part, mixed metal element dopant part and second metal element dopant part, mixed metal dopant part and the second metal dopant part exist in a 1:2 weight ratio, mixed metal dopant part comprises vanadium element, lanthanum element and tantalum element, mixed metal dopant is doped by pulse laser deposition method, the pulse laser deposition method comprises the following steps of mixing vanadium metal, lanthanum metal and tantalum metal with 99% purity of metal zinc according to a ratio, ball milling for 24h, presintering for 4-8 h at 600-700 ℃, pressing into a wafer with diameter of 30-50mm and thickness of 3mm under 20-30MPa pressure, sintering for 4-8 h at 1000-1200 ℃ to obtain a metal zinc target material, the substrate is silicon single crystal, loading the metal zinc target material into a pulse laser deposition rotary target position, fixing the substrate on a rotatable sample holder, introducing buffer gas of argon and oxygen and zinc metal, and the substrate has a distance between 20-8 h at 1200 ℃, and the substrate has a laser power of 380-80 Hz, a laser doping frequency of 380-300 Hz, and a doping frequency of 3625 Hz;
the indium element is doped by a radio frequency reactive sputtering method, wherein the radio frequency reactive sputtering method comprises the following steps of pre-vacuum of 5-6 Pa before sputtering, a substrate of th mixed metal-doped zinc oxide obtained by a pulse laser deposition method, a metal zinc target with the diameter of 10mm and the purity of more than 99.99 percent, a sputtering reaction gas of mixed gas of argon and oxygen, a distance between the substrate and the metal zinc target of 50mm, the substrate temperature of 100 ℃ and 300 ℃, the sputtering power of 60-200W, the sputtering pressure of 1-3.8 Pa and the sputtering time of 1-2 h.
Specific example 3:
composition for a semiconductor sensor doped based on zinc oxide, the composition comprises more than 99 wt% of a zinc part, a mixed metal element dopant part and a second metal element dopant part, a mixed metal dopant part and the second metal dopant part exist in a weight ratio of 0.5:2.5, a mixed metal dopant part comprises vanadium, lanthanum, calcium and tantalum, a mixed metal dopant is doped by a pulse laser deposition method, the pulse laser deposition method comprises the steps of mixing vanadium, lanthanum, tantalum and calcium with metal zinc with a purity of more than 99% in proportion, ball milling for 24h, presintering for 4-8 h at 600-700 ℃, pressing into a wafer with a diameter of 30-50mm and a thickness of 3mm under a pressure of 20-30MPa, sintering for 4-8 h at 1000-1200 ℃ to obtain metal zinc, a substrate is a silicon single crystal, pulse laser depositing a metal zinc target rotating, loading the substrate on a rotatable sample holder, loading argon and oxygen gas, introducing the argon and oxygen gas into the substrate, and obtaining a mixed metal substrate with a laser power of 80 Hz of 80-300 Hz, and a laser substrate frequency of 80-300 Hz, wherein the substrate is a laser power of a laser deposition frequency of 1-300 Hz;
the indium element is doped by a radio frequency reactive sputtering method, wherein the radio frequency reactive sputtering method comprises the following steps of pre-vacuum of 5-6 Pa before sputtering, a substrate of th mixed metal-doped zinc oxide obtained by a pulse laser deposition method, a metal zinc target with the diameter of 10mm and the purity of more than 99.99 percent, a sputtering reaction gas of mixed gas of argon and oxygen, a distance between the substrate and the metal zinc target of 50mm, the substrate temperature of 100 ℃ and 300 ℃, the sputtering power of 60-200W, the sputtering pressure of 1-3.8 Pa and the sputtering time of 1-2 h.
The above-mentioned embodiments are only for convenience of description, and are not intended to limit the present invention in any way, and those skilled in the art will understand that the technical features of the present invention can be modified or changed by other equivalent embodiments without departing from the scope of the present invention.
Claims (3)
- A composition for a zinc oxide-doped based semiconductor sensor, wherein the composition comprises greater than 99 wt% of a zinc portion, a mixed metal element dopant portion, and a second metal element dopant portion;said th mixed metal dopant portion and said second metal dopant portion being present in a weight ratio of 0.5-1: 2-2.5;the mixed metal dopant moiety has a chemical bond length in the zinc oxide unit cell produced by the metal element and oxygen element that is less than the bond length of the zinc element and oxygen element;the second metal dopant part has a chemical bond length produced by metal elements and oxygen elements in the zinc oxide unit cell larger than the bond length of the zinc elements and the oxygen elements;the th mixed metal dopant part comprises vanadium pentoxide and lanthanum oxide;the mixed-metal dopant moiety further includes groups of metal elements that increase the unit cell volume of zinc oxide when doped;the mixed metal dopant is doped by a pulse laser deposition method, the pulse laser deposition method comprises the following steps of mixing and ball-milling metals in mixed metal dopant and zinc with the purity of more than 99% according to a proportion for 24 hours, presintering at 600-700 ℃ for 4-8 hours, pressing under the pressure of 20-30MPa into a wafer with the diameter of 30-50mm and the thickness of 3mm, and sintering at 1000-1200 ℃ for 4-8 hours to obtain a metal zinc target material, wherein the substrate is a silicon single crystal, the metal zinc target material is arranged in a pulse laser deposition rotating target position, the substrate is fixed on a self-rotating sample holder, the distance between a buffer gas substrate with argon and oxygen and the metal zinc target is 20mm, the substrate temperature is 380-550 ℃, the laser power density is 1-3, the laser pulse width is 25ns, the frequency is 1-50 Hz, and the power is 30-300W to obtain mixed metal-doped zinc oxide;the second metal element dopant is partially doped by a radio frequency reactive sputtering method, wherein the radio frequency reactive sputtering method comprises the following steps of under the sputtering condition that the pre-vacuum before sputtering is 5-6 Pa, the substrate is th mixed metal doped zinc oxide obtained by a pulse laser deposition method, the sputtering target is a metal zinc target with the diameter of 10mm and the purity of more than 99.99%, the sputtering reaction gas is mixed gas of argon and oxygen, the distance between the substrate and the metal zinc target is 50mm, the substrate temperature is 100-300 ℃, the sputtering power is 60-200W, the sputtering pressure is 1-3.8 Pa, and the sputtering time is 1-2 h.
- 2. The composition for use in a semiconductor sensor doped with zinc oxide according to claim 1, wherein the mixed metal dopant contains group of tantalum or calcium as the metal element that increases the unit cell volume of zinc oxide.
- 3. The composition for a semiconductor sensor based on zinc oxide doping according to claim 1, wherein the second metal dopant is indium.
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| CN201910937329.3A CN110735114A (en) | 2019-09-30 | 2019-09-30 | composition for semiconductor sensor based on zinc oxide doping |
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Application publication date: 20200131 |