CN109100900A - A kind of HfO2The application method of base ferroelectric material - Google Patents

A kind of HfO2The application method of base ferroelectric material Download PDF

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CN109100900A
CN109100900A CN201810810074.XA CN201810810074A CN109100900A CN 109100900 A CN109100900 A CN 109100900A CN 201810810074 A CN201810810074 A CN 201810810074A CN 109100900 A CN109100900 A CN 109100900A
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hfo
ferroelectric material
linear
base ferroelectric
optical
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CN109100900B (en
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毕磊
黄飞
秦俊
邓龙江
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University of Electronic Science and Technology of China
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/3558—Poled materials, e.g. with periodic poling; Fabrication of domain inverted structures, e.g. for quasi-phase-matching [QPM]

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)

Abstract

The invention belongs to semiconductor devices and nonlinear optics application field, in particular to a kind of HfO2The application method of base ferroelectric material.The present invention will be used for the HfO of semiconductor storage industry2Base ferroelectric material is applied to nonlinear optics component as nonlinear optical material, has a spontaneous polarization properties using ferroelectric material, and spontaneous polarization can carry out inverting with external electric field and still retainable congenital non-linear optical property when power is off.Also utilize designed device metal structure by electric field local in ferroelectricity HfO2Layer has excellent CMOS compatibility and Miniaturizable ability outstanding, has higher stability in wider array of temperature range to obtain stronger second harmonic excitation.Can be applied to electric light open the light, the fields such as laser frequency-modulation, sensing detection.There is the optical component of semiconductor compatibility and Miniaturizable to have great importance development.

Description

A kind of HfO2The application method of base ferroelectric material
Technical field
The invention belongs to semiconductor devices and nonlinear optics application field, in particular to a kind of HfO2Base ferroelectric material Application method.
Background technique
Nonlinear optics component is widely used in the fields such as optic communication and integrated optics, such as utilizes various non-linear crystalline substances Body be made into electrooptical switching and realize laser modulation, using secondary and triple-frequency harmonics generation, second order and three ranks it is optical and frequency Realize that the conversion of laser frequency, acquisition are as short as ultraviolet, vacuum ultraviolet, the long various laser to far infrared with difference frequency；Meanwhile it can lead to The upper conversion of realization infrared frequency is crossed to overcome the difficulty in terms of infrared receiver.Device integration is required with people It is continuously improved, finding a kind of nonlinear optical material with semiconductor compatibility, Miniaturizable, low-power consumption becomes especially to weigh It wants.
Although the known material with non-linear behaviour is numerous, metal oxide more by the favor of industry, Traditional common nonlinear crystalline material has lithium niobate (LiNbO3), barium titanate (BTO) and potassium dihydrogen phosphate (KDP).But this The compatible sexuality of the semiconductor of quasi-tradition material is bad, and power consumption is larger, and does not have good miniaturization capability.Therefore in the industry Personage have been devoted to find new nonlinear optical material with promoted its these in terms of performance, meet the need of production development It asks.
Find the HfO of doping for the first time from T.Mikolajick in 2011 etc.2Since film has ferroelectric properties, HfO2Base iron Electric material is because of preparation process and CMOS is completely compatible, Miniaturizable is widely used in semiconductor storage industry due to the characteristics of, and It is pursued in the industry.But the application for this material in non-linear optical field but has not been reported.
Summary of the invention
It is in view of the above problems or insufficient, to solve the compatible sexuality of existing nonlinear optical material semiconductor not Problem good, power consumption is larger and miniaturization capability is insufficient, the present invention provides a kind of HfO2The application method of base ferroelectric material.
A kind of HfO2The application method of base ferroelectric material: by HfO2Base ferroelectric material is applied to as nonlinear optical material The preparation of nonlinear optics component.
Further, the HfO2Base ferroelectric material is the HfO of zirconium, aluminium, silicon, yttrium or multi-element doping2Base ferroelectric material body System.
Further, the HfO2Base ferroelectric material is as nonlinear optical material in use, utilizing designed device Metal structure, dielectric structure or optical waveguide structure are by electric field local in ferroelectricity HfO2Layer.
Further, the nonlinear optics component is non-linear in second nonlinear optic and electrooptic effect field Fiber waveguide device, non-linear photon crystal device, nonlinear surface plasmon device, non-linear metamaterial are non-linear Super structure surface and non-linear all dielectric resonance structure.
HfO2Base ferroelectric material nonlinear optics component the preparation method is as follows:
Step 1, the HfO that amorphous doping is grown in TiAlN thin film substrate2Film；
Step 2, the HfO obtained in step 12TiN top electrode is grown on film and carries out short annealing processing, obtains polycrystalline The HfO of doping2Ferroelectric thin film；
Step 3, the HfO for adulterating polycrystalline made from step 22Ferroelectric thin film is placed in hydrogen peroxide, and etching removes top layer TiN；
Step 4 designs corresponding light using the second harmonic wave band that Comsol computer analog software generates as needed Learn structure size.
Step 5 produces corresponding light according to the optical texture size that computer analog goes out using electron beam lithography EBL technology Learn figure.
Step 6 deposits gold using electron beam evaporation technique in the figure made from step 5.
The sample that metallic gold has been deposited in step 6 is placed in acetone soln the removing for carrying out photoresist by step 7, is completed Whole preparations of second nonlinear optic device.
The present invention will be used for the HfO of semiconductor storage industry2Base ferroelectric material is applied to non-as nonlinear optical material Linear optics component has spontaneous polarization properties using ferroelectric material, and spontaneous polarization can be inverted simultaneously with external electric field Still retainable congenital non-linear optical property when power is off.Based on ferroelectricity HfO2The nonlinear optics feature itself having, and Using designed metal structure by electric field local in ferroelectricity HfO2Layer has excellent to obtain stronger second harmonic excitation Different CMOS compatibility and Miniaturizable ability outstanding.Compared with organic polymer or organic crystal, inorganic ferroelectric material exists There is higher stability in wider array of temperature range.Can be applied to electric light open the light, the fields such as laser frequency-modulation, sensing detection.It is right Developing, there is the optical component of semiconductor compatibility and Miniaturizable to have great importance.
In conclusion nonlinear optics component prepared by the present invention be provided simultaneously with CMOS compatibility and it is outstanding can be small Type ability can operate with non-linear optical field highly integrated on silicon, have in wider array of temperature range higher steady It is qualitative.
Detailed description of the invention
Fig. 1 is preparation flow figure of the present invention；
Fig. 2 is the XRD spectrum of embodiment；
Fig. 3 is the ferroelectric hysteresis loop characteristic map of embodiment；
Fig. 4 is the optical grating construction map that embodiment carries out non-linear test preparation；
Fig. 5 is that optical device made from embodiment reflects spectrogram；
Fig. 6 is second harmonic excitation characteristic pattern of the embodiment when incident laser power is 15.41mW, incidence angle is 45 degree Spectrum；
Fig. 7 is HfO2Base material not the ferroelectric reference examples when incident laser power is 15.41mW, incidence angle is 45 degree two Subharmonic excites characteristic spectrum；
Fig. 8 is the second order nonlinear coefficient that embodiment is calculated.
Specific embodiment
The present invention is further elaborated with reference to the accompanying drawings and examples.
It is 3.8mol.% with yttrium content, with a thickness of the ferroelectricity HfO of 20nm2Film is embodiment to specific in the present invention Step is described in detail:
Step 1: magnetron sputtered deposition technology is used, in SiO2The TiAlN thin film of one layer of 100nm is deposited in/Si substrate first As hearth electrode.
Take SiO2/ Si substrate cleans its surface with organic solvent and deionized water, removes impurity.Organic solvent includes Acetone and ethyl alcohol.Successively silicon wafer dipping is placed in ultrasonic clean instrument with acetone, ethyl alcohol, deionized water and is cleaned by ultrasonic each 3 Minute, and immediately with being dried with nitrogen.
A, by the SiO after cleaning2/ Si substrate is placed in vacuum chamber above target, and target-substrate distance is fixed as 55mm, substrate temperature It is increased to 300 DEG C；
B, it is passed through 99.999% argon gas, control pressure starts depositing TiN hearth electrode after 0.13Pa, pre-sputtering 5min；
C, after growth, sample is down to room temperature under vacuum conditions, takes out from vacuum chamber.
Step 2: using pulsed laser deposition PLD technology, 20nm yttrium is grown on the TiN hearth electrode that step 1 obtains sample The HfO of doping2Film.
A, sample obtained in step 1 is placed in vacuum chamber above target, target-substrate distance is fixed as 55mm, substrate temperature liter Up to 100 DEG C；
B, it is passed through 99.999% oxygen, control oxygen is pressed in 1Pa, wavelength is used to rotate for laser (KrF) ablation of 248nm Target material surface, laser energy 2.5J/cm2, carry out HfO2Target and the exchange of yttrium oxide target are practiced shooting, wherein laser hits HfO2 The pulse frequency of target is 5Hz, under strike 36；The pulse frequency for hitting yttrium oxide target is 2Hz, under strike 1.So circulation 28 Time, it obtains with a thickness of 20nm, yttrium content is the amorphous HfO of 3.8mol.%2Film.
Step 3: using PLD technology, the amorphous made from step 2 mixes the HfO of yttrium2The TiN of growth in situ 30nm on film Top electrode.A, after step 2, stopping is passed through oxygen, so that cavity is kept high vacuum state, by substrate temperature in 5 minutes by 100 DEG C at the uniform velocity rise to 200 DEG C；
B, it is passed through 99.999% argon gas, air pressure is maintained at 0.5Pa, and wavelength is used to rotate for laser (KrF) ablation of 248nm Nitridation titanium target material surface, laser energy 4J/cm2, laser pulse frequency 10Hz grows the TiN top electrode of 30nm；
C, after growth, sample drops to room temperature in high vacuum condition natural cooling, takes out from vacuum chamber.
Step 4: using short annealing RTA technology, short annealing processing is carried out to the sample that step 3 obtains, obtains polycrystalline The HfO for mixing yttrium2Ferroelectric thin film.The sample taken out in step 3 is placed in quick anneal oven, 99.999% nitrogen, gas are passed through Pressure is maintained at 2mTorr, and 30s is warming up to 600 DEG C, keeps the temperature 1 minute, cooled to room temperature.Sample is taken out, is obtained with ferroelectricity The polycrystalline HfO of property2Film.
Step 5: sample obtained in step 4 being steeped in the hydrogen peroxide that temperature is 60 DEG C, wash away top layer TiN electrode, revealed Complete HfO out2Ferroelectric thin film.
Step 6: as it is desirable that the optical device being prepared can obtain the second harmonic excitation at 400nm, therefore logical The adjustment that Comsol simulation software carries out height, width, periodic dimensions to the optical grating construction of design is crossed, so that the grating designed Structure can generate resonance in 800nm wave band.Finally determining metal grating height is 30nm, width 50nm, and the period is 230nm。
Step 7: according to the computer artificial result in step 6, preparing width using electron beam lithography EBL technology is 50nm, the optical grating construction that the period is 230nm.
It is coated with one layer of PMMA photoresist in sample surfaces, it is about 100nm thick that the revolving speed for adjusting photoresist spinner, which obtains thickness, Photoresist.The sample for being coated with photoresist is placed in scanning electron microscope, selection uses 100 times of micro- lens head and adjusts Section starts from figure according to designed dimension of picture to suitable electronic beam current.
Step 8: after step 7 designs optical figuring, sample being placed in electron beam evaporation cavity, deposition thickness is The gold of 30nm.
Step 9: the sample for having deposited gold in step 8 being placed in acetone soln, remaining PMMA photoresist is removed.Again will Sample is respectively placed in alcohol and deionized water, finally dries up surface with nitrogen air gun.So far whole systems of optical device are completed Standby process.
To HfO made from embodiment2Ferroelectric material carries out second harmonic challenge test, and used laser power is The incident angle of 15.41mW, laser are 45 degree:
HfO obtained2Test results are shown in figure 2 by the XRD of ferroelectric material crystal phase.From figure 2 it can be seen that obtained HfO2The principal crystalline phase of ferroelectric material is orthorhombic phase, and it is non-central right necessary to nonlinear optical material to illustrate that the material has had Claim structure.
HfO made from embodiment2The ferroelectric hysteresis loop characteristic test result of ferroelectric material is as shown in Figure 3.It can from Fig. 3 Out, the remanent polarization 2Pr of the material is about 20 μ C/cm2, there is good ferroelectric properties.
Ferroelectricity HfO made from embodiment2The optical grating construction of base optical device is as shown in Figure 4.The width of grating is 50nm, light Grid with a thickness of 30nm, the period of grating is 230nm.
It is as shown in Figure 5 that optical device made from embodiment reflects spectrogram.As can be seen from Figure 5 the optical device prepared In 800nm or so, this is consistent with resonance wavelength with computer artificial result, illustrates that the actual error of embodiment is smaller.
HfO made from embodiment2Ferroelectric material is 800nm in wavelength, and power 15.41mW, incidence angle is 45 degree of laser Second harmonic excitation signal under irradiation is as shown in Figure 6.As can be seen from Figure 6 there is maximum value at 400nm in signal, meets Second harmonic excites the feature of (SHG), illustrates HfO made from embodiment2Ferroelectric material has second nonlinear feature.
HfO2Base material not the ferroelectric reference examples are 800nm in wavelength, and power 15.41mW, incidence angle is that 45 degree of laser shine Second harmonic excitation signal under penetrating is as shown in Figure 7.As can be seen from Figure 7 there is maximum value at 400nm in signal, and numerical value is big About 400cps.Signal maximum in Fig. 6 at 400nm is about 1200cps, is 3 times in Fig. 7.Illustrate HfO obtained2Base Ferroelectric material embodiment shows more excellent second nonlinear performance, is suitable for second nonlinear optic field.
HfO made from embodiment2The second order nonlinear coefficient calculated result of ferroelectric material is as shown in figure 8, about 9.5pm/ V.Illustrate that embodiment obtained has good second order nonlinear coefficient.
By above-mentioned test it can be proved that HfO2Ferroelectric material has good second nonlinear performance, is based on HfO2Iron The structure of electric material design can show stronger second harmonic excitation.Therefore HfO2Ferroelectric material can operate with electric light and open The non-linear optical fields such as pass, laser frequency-modulation, sensing detection.And it has been provided simultaneously with CMOS compatibility and Miniaturizable outstanding Ability can operate with non-linear optical field highly integrated on silicon, have higher stability in wider array of temperature range.

Claims (5)

1. a kind of HfO2The application method of base ferroelectric material, it is characterised in that: by HfO2Base ferroelectric material is as nonlinear optics material Material is applied to nonlinear optics component and prepares.
2. HfO as described in claim 12The application method of base ferroelectric material, it is characterised in that: the HfO2Base ferroelectric material is Zirconium, aluminium, silicon, yttrium or multi-element doping HfO2Base ferroelectric material system.
3. HfO as described in claim 12The application method of base ferroelectric material, it is characterised in that: the HfO2Base ferroelectric material is made For nonlinear optical material in use, using designed device metal structure, dielectric structure or optical waveguide structure by electric field office Domain is in ferroelectricity HfO2Layer.
4. HfO as described in claim 12The application method of base ferroelectric material, it is characterised in that: the nonlinear optics component For the non-linear optical waveguide device in second nonlinear optic and electrooptic effect field, non-linear photon crystal device is non-linear Surface plasmons device, non-linear metamaterial, non-linear super structure surface and non-linear all dielectric resonance structure.
5. HfO as described in claim 12The application method of base ferroelectric material, the preparation method of specific device for non-linear optical is such as Under:
Step 1, the HfO that amorphous doping is grown in TiAlN thin film substrate2Film；
Step 2, the HfO obtained in step 12TiN top electrode is grown on film and carries out short annealing processing, obtains polycrystalline doping HfO2Ferroelectric thin film；
Step 3, the HfO for adulterating polycrystalline made from step 22Ferroelectric thin film is placed in hydrogen peroxide, and etching removes the TiN of top layer；
Step 4 designs corresponding optics knot using the second harmonic wave band that Comsol computer analog software generates as needed Structure size；
Step 5 produces corresponding optical picture according to the optical texture size that computer analog goes out using electron beam lithography EBL technology Shape；
Step 6 deposits gold using electron beam evaporation technique in the figure made from step 5；
The sample that metallic gold has been deposited in step 6 is placed in acetone soln the removing for carrying out photoresist by step 7, completes second order Whole preparations of device for non-linear optical.
CN201810810074.XA 2018-07-23 2018-07-23 Application method of HfO 2-based ferroelectric material Active CN109100900B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109979811A (en) * 2019-03-20 2019-07-05 电子科技大学 A kind of preparation method of tantalum doping hafnium oxide novel ferroelectric material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104810269A (en) * 2014-01-27 2015-07-29 格罗方德半导体公司 Semiconductor device with ferooelectric hafnium oxide and method for forming semiconductor device
CN106783531A (en) * 2016-11-23 2017-05-31 电子科技大学 A kind of HfO2The application method of base ferroelectric material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104810269A (en) * 2014-01-27 2015-07-29 格罗方德半导体公司 Semiconductor device with ferooelectric hafnium oxide and method for forming semiconductor device
CN106783531A (en) * 2016-11-23 2017-05-31 电子科技大学 A kind of HfO2The application method of base ferroelectric material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
J. PRICE ET AL: "Resonant photoionization of defects in Si/SiO2 /HfO2 film stacks observed by second-harmonic generation", 《APPLIED PHYSICS LETTERS 》 *
RAN JIANG ET AL: "HfO2-based ferroelectric modulator of terahertz waves with graphene metamaterial", 《CHIN. PHYS. B 》 *
TONY SCHENK ET AL: "Electric Field Cycling Behavior of Ferroelectric Hafnium Oxide", 《ACS APPLIED MATERIALS & INTERFACES》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109979811A (en) * 2019-03-20 2019-07-05 电子科技大学 A kind of preparation method of tantalum doping hafnium oxide novel ferroelectric material

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