CN108400083A - A kind of method that hafnia film stablizes transition group oxide surface conductive layer - Google Patents
A kind of method that hafnia film stablizes transition group oxide surface conductive layer Download PDFInfo
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- CN108400083A CN108400083A CN201810038056.4A CN201810038056A CN108400083A CN 108400083 A CN108400083 A CN 108400083A CN 201810038056 A CN201810038056 A CN 201810038056A CN 108400083 A CN108400083 A CN 108400083A
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- conductive layer
- transition group
- surface conductive
- oxide surface
- group oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/024—Group 12/16 materials
- H01L21/02403—Oxides
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02425—Conductive materials, e.g. metallic silicides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02554—Oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
Abstract
The invention belongs to semiconductor device processing technology fields, a kind of method of hafnia film stabilization transition group oxide surface conductive layer is provided, to solve the unstable technical problem of ion bombardment transition group oxide surface conductive layer, the present invention will cover one layer of hafnia film, as passivation layer on the transition group oxide surface conductive layer.Hafnia film is as a kind of surface passivation material; there is wide band gap (5.7eV), higher dielectric constant (about 25), higher hardness and high chemical stability compared to other materials; there are preferable thermodynamic stability and good lattice matching property; it is good to the protective value of device, the stability of transition group oxide surface conductive layer can be greatly improved；Meanwhile hafnia film of the present invention is prepared using pulsed laser deposition technique, preparation process has pollution-free, easy to control, can accurately control stoichiometry, it is simple for process, flexibility is big the advantages that.
Description
Technical field
The invention belongs to semiconductor device processing technology fields, and in particular to a kind of stabilization transition based on hafnia film
The method of race's oxide surface conductive layer.
Background technology
With industrial digital, intelligent development, sensor is in mechanical processing, temperature monitoring, wearable device and wisdom
It is widely used in traffic.Transition group oxide is as wherein important sensing element, all the time all by extensive
Research.Transition group oxide itself is a kind of insulating materials, has perovskite structure, is modified by surface and physics can be achieved
The regulation and control of performance, ion implanting are that surface is modified a kind of common method, can be formed by ion bombardment transition group oxide
Surface conductive layer has many advantages, such as that surface conductance is controllable, mobility is high, easy to operate；Photoelectric sensor, gas sensor,
Piezoelectric transducer, volatile memory and HEMT devices etc. have been widely used.
It can form the conductive layer of particular surface resistance using ion bombardment transition group oxide surface, but surface conductive layer
Resistance persistently increases with time change, and stability is insufficient, seriously affects device application.It is asked to solve conductive layer stability
Topic, it is necessary to device architecture be advanced optimized on the basis of existing.Surface passivation is a kind of feasible ameliorative way,
Surface contamination, while the dangling bonds that passivated surface is more active can be prevented, the reliability and stability of device is improved.Often at present
Surface passivation material has aluminium oxide, silicon nitride etc., but silicon nitride can cause the decline of carrier mobility and dielectric is normal
Number is relatively low, and only 7 or so；It is only 9 or so that the relative dielectric constant of aluminium oxide is also very low, equally has the problem.
Invention content
It is an object of the invention in view of the deficiencies in the prior art and insufficient, a kind of hafnia film is provided and is stablized
The method of transition group oxide surface conductive layer solves ion bombardment transition group oxide surface using the method for surface passivation
The unstable technical problem of conductive layer, improves the stability of surface conductive layer.
In order to achieve the above-mentioned object of the invention, the technical solution that this programme uses for：
A kind of method that hafnia film stablizes transition group oxide surface conductive layer, which is characterized in that the transition group
One layer of hafnia film is covered on oxide surface conductive layer, as passivation layer.
Further, the thickness of the hafnia film is 100~150nm.
Further, the hafnia film is prepared using pulsed laser deposition technique, is as follows：
In transition group oxide surface conductive layer upper surface pulse laser frequency is adjusted using oxidation hafnium ceramic as target
Rate is 1~5Hz, underlayer temperature is room temperature, oxygen pressure is 5~10Pa, and sedimentation time is about 10~20 minutes, is prepared into thickness
It is covered in transition group oxide surface conductive layer upper surface for 100~150nm hafnia films.
The beneficial effects of the present invention are：
The present invention provides a kind of method of hafnia film stabilization transition group oxide surface conductive layer, and hafnia film is made
For a kind of surface passivation material, compared to other materials have wide band gap (5.7eV), higher dielectric constant (about 25), compared with
High hardness and high chemical stability have preferable thermodynamic stability and good lattice matching property, to the guarantor of device
It is good to protect performance, the stability of transition group oxide surface conductive layer can be greatly improved；Meanwhile hafnia film of the present invention uses
Prepared by pulsed laser deposition technique, preparation process has pollution-free, easy to control, can accurately control stoichiometry, simple for process,
The advantages that flexibility is big.
Description of the drawings
The structural schematic diagram of Fig. 1 embodiment of the present invention.
Fig. 2 embodiment of the present invention obtains the stability diagram of strontium titanates surface conductive layer under room temperature.
Specific implementation mode
The present invention is described in further detail with reference to the accompanying drawings and examples.
The method that a kind of hafnia film of the present embodiment stablizes transition group oxide surface conductive layer, structure such as Fig. 1 institutes
Show, to aoxidize hafnium ceramic as target in the present embodiment, using 5mm*5mm, (100) crystal orientation single-crystal strontium titanate as substrate, it is specific to walk
It is rapid as follows：
Step 1：It is that substrate is for use with the single-crystal strontium titanate of acetone/alcohol washes 5mm*5mm, (100) crystal orientation；
Step 2：Utilize Ar+Bombard above-mentioned single-crystal strontium titanate substrate.Substrate is fixed on objective table, is then taken out cavity true
Sky causes 3.0 × 10-4Pa makes pressure be maintained at 2.0 × 10 hereinafter, be passed through pure argon into cavity again-2Pa, after stable gas pressure,
Adjust bombardment parameters：Line voltage battery parameter value is 300V, and ion beam current parameter value is 10.0mA, and accelerating potential parameter value is
60V；Bombardment time is to prepare strontium titanates surface conductive layer in 30 minutes；
Step 3：Film is prepared using pulsed laser deposition technique：Pulse is used right over the surface conductive layer of step 2
Laser deposition technique deposit hafnium oxides film；
Detailed process is：First in the chamber of pulse laser thin film deposition system by hafnium oxide target (a diameter of 25mm,
Thickness is 5mm, purity 99.99%) it is fixed on target platform, and will be through Ar+Strontium titanates after bombardment is fixed on substrate table；It will
The chamber is evacuated to 3.0 × 10-4Pa makes oxygen pressure be maintained at 8Pa, waits for gas hereinafter, be then passed through purity oxygen into chamber
After pressure is stablized, start KrF excimer lasers (wavelength 248nm), laser beam is gathered on target, starts deposition film；
Pulse laser frequency is 2 hertz；Underlayer temperature is room temperature, and the thickness of deposit hafnium oxides is~100nm；
Step 4：Test electrode Ti/Pt is prepared using magnetron sputtering：Pass through photoetching, development, metallization (magnetron sputtering) etc.
Technique prepares Ti (10nm)/Pt (50nm) electrode；The electrode is for testing above-mentioned surface conductive layer resistance, and wherein Ti makees
For the buffer layer between transition group oxide and Pt metal, enhance the adhesive force of Pt metal.
The stability diagram for the surface conductive layer of strontium titanates under room temperature that above-described embodiment as shown in Figure 2 obtains, can by figure
See, without HfO2Passivation layer does protective layer, and the increase of the surface conductive layer resistance of strontium titanates at any time is linearly increasing, in t=
Resistance is about 3 times of initial resistance when 100h, and journey continuous upward trend；After lining hafnia film protection, metatitanic acid
Strontium surface conductive layer resistance is as the change rate of time is within 3%；It can be seen that hafnia film stablizes titanium strontium surface conductance
Layer electricity group is with obvious effects.
The above description is merely a specific embodiment, any feature disclosed in this specification, except non-specifically
Narration, can be replaced by other alternative features that are equivalent or have similar purpose；Disclosed all features or all sides
Method or in the process the step of, other than mutually exclusive feature and/or step, can be combined in any way.
Claims (3)
1. a kind of method that hafnia film stablizes transition group oxide surface conductive layer, which is characterized in that the transition group oxygen
One layer of hafnia film is covered on compound surface conductive layer, as passivation layer.
2. stablizing the method for transition group oxide surface conductive layer by hafnia film described in claim 1, which is characterized in that institute
The thickness for stating hafnia film is 100~150nm.
3. stablizing the method for transition group oxide surface conductive layer by hafnia film described in claim 1, which is characterized in that institute
It states hafnia film to prepare using pulsed laser deposition technique, be as follows：
In transition group oxide surface conductive layer upper surface, using oxidation hafnium ceramic as target, it is 1 to adjust pulse laser frequency
~5Hz, underlayer temperature are room temperature, oxygen pressure is 5~10Pa, and sedimentation time is about 10~20 minutes, and it is 100 to be prepared into thickness
~150nm hafnia films are covered in transition group oxide surface conductive layer upper surface.
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| CN201810038056.4A CN108400083A (en) | 2018-01-16 | 2018-01-16 | A kind of method that hafnia film stablizes transition group oxide surface conductive layer |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752236A (en) * | 2009-10-26 | 2010-06-23 | 南京大学 | Atomic layer deposition Al2O3/HfO2 method for regulating energy band offset between GaAs semiconductor and gate dielectric |
| US20150303311A1 (en) * | 2012-12-18 | 2015-10-22 | Gang Yu | Metal oxide tft with improved stability and mobility |
| US20160358835A1 (en) * | 2015-06-03 | 2016-12-08 | Asm Ip Holding B.V. | Methods for semiconductor passivation by nitridation after oxide removal |
-
2018
- 2018-01-16 CN CN201810038056.4A patent/CN108400083A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752236A (en) * | 2009-10-26 | 2010-06-23 | 南京大学 | Atomic layer deposition Al2O3/HfO2 method for regulating energy band offset between GaAs semiconductor and gate dielectric |
| US20150303311A1 (en) * | 2012-12-18 | 2015-10-22 | Gang Yu | Metal oxide tft with improved stability and mobility |
| US20160358835A1 (en) * | 2015-06-03 | 2016-12-08 | Asm Ip Holding B.V. | Methods for semiconductor passivation by nitridation after oxide removal |
Non-Patent Citations (1)
| Title |
|---|
| SHAOQING REN ET AL.: "《Resistive switching and electrical control of ferromagnetism in a Ag/HfO2/Nb:SrTiO3/Ag resistive random access memory (RRAM) device at room temperature》", 《J. PHYS.: CONDENS. MATTER》 * |
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