CN106783531A - 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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Publication number
CN106783531A
CN106783531A CN201611033497.2A CN201611033497A CN106783531A CN 106783531 A CN106783531 A CN 106783531A CN 201611033497 A CN201611033497 A CN 201611033497A CN 106783531 A CN106783531 A CN 106783531A
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hfo
ferroelectric material
application method
base ferroelectric
radiation
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毕磊
黄飞
王艳
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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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
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02181—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G27/00—Compounds of hafnium
    • C01G27/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Semiconductor Memories (AREA)

Abstract

The invention belongs to semiconductor devices and space technology application field, more particularly to a kind of HfO2The application method of base ferroelectric material.The invention provides HfO2Base ferroelectric material application method, based on HfO2Base ferroelectric material has extremely strong Radiation hardness, can ensure that device normally runs for a long time under radiation environment.Therefore the extreme operating environments of nuclear industry, space flight and the such radiation environment high of core hospitality industry be can be applied to.Nonvolatile ferroelectric memory to development with Radiation hardness and its have great importance in the application of the industries such as Aero-Space, nuclear industry, hospitality industry.

Description

A kind of HfO2The application method of base ferroelectric material
Technical field
The invention belongs to semiconductor devices and space technology application field, more particularly to a kind of HfO2Base ferroelectric material makes Use method.
Background technology
Nonvolatile semiconductor memory member is widely used in area information storage (random access memory such as in computer, mobile phone), In the fields such as food security irradiation preservation, Radiation Sterilization of Medical Products sterilization, radiation chemical engineering, Aero-Space and nuclear industry, spoke high Memory device can be caused to damage according to environment, ultimately result in component failure.Therefore, in order to ensure memory device in radiation environment Remain to be reliably completed predetermined function, seek high speed, low-power consumption, highly anti-radiation ability novel memory devices it is particularly important.
Ferroelectric material is that a class has spontaneous polarization properties, and spontaneous polarization can be inverted and in power-off with external electric field When still retainable dielectric material.Compared with based on electron charge come the dielectric material of storage information, ferroelectric material is in electromagnetic wave With under the radiation of various rays have stability higher.
Although it is known with ferroelectric material more than 500 kinds, oxide is more favored by industrial quarters, tradition Conventional ferroelectric material have lead zirconate titanate (PZT), strontium bismuth tantalate (SBT) and mix the bismuth tantalate (BLT) of lanthanum.Due to food security For Flouride-resistani acid phesphatase in irradiation preservation, Radiation Sterilization of Medical Products sterilization, radiation chemical engineering, Aero-Space and these fields of nuclear industry It is required that high, at present using traditional ferroelectric material of this kind of technology maturation of PZT, SBT and BLT, but this kind of traditional material is anti- Irradiation ability is not good, and professional is devoted to being lifted always the performance of its this respect.
Find the HfO of doping first from T.Mikolajick in 2011 etc.2Since film has ferroelectric properties, HfO2Base iron Electric material because preparation technology and CMOS is completely compatible, Miniaturizable the characteristics of be widely used in semicon industry, and be based on This is pursued in the industry.
The content of the invention
For above-mentioned problem or deficiency, the invention provides a kind of HfO2The application method of base ferroelectric material.
HfO2The preparation method of base ferroelectric material is as follows：
Step 1, in substrate depositing TiN thin film first as hearth electrode；
Step 2, the HfO that growth amorphous adulterates in the TiAlN thin film that step 1 is obtained2Film；
Step 3, the HfO in amorphous doping obtained in step 22TiN top electrodes are grown on film；
Step 4, using short annealing RTA technologies, the sample obtained to step 3 carries out short annealing treatment, obtains polycrystalline The HfO of doping2Ferroelectric thin film.
The HfO2Base ferroelectric material is applied to extreme operating environments, such as radiation environment high.
The invention provides a kind of HfO2The application method of base ferroelectric material, based on HfO2Base ferroelectric material has extremely strong Radiation hardness, therefore extreme operating environments are can be applied to, such as radiation environment high.
Brief description of the drawings
Fig. 1 is preparation flow figure of the present invention；
Fig. 2 is XRD spectrum of the embodiment after various dose irradiation；
Fig. 3 is I-V characteristic collection of illustrative plates of the embodiment after various dose irradiation；
Fig. 4 is C-V characteristic collection of illustrative plates of the embodiment after various dose irradiation；
Fig. 5 is ferroelectric hysteresis loop characteristic collection of illustrative plates of the embodiment after various dose irradiation；
Fig. 6 is fatigue properties of the embodiment after various dose irradiation under 1.3MV/cm field intensity；
Fig. 7 is fatigue properties of the embodiment after various dose irradiation under 1.4MV/cm field intensity；
Fig. 8 is fatigue properties of the embodiment after various dose irradiation under 1.6MV/cm field intensity；
Fig. 9 is fatigue properties of the embodiment after various dose irradiation under 1.8MV/cm field intensity；
Figure 10 is the ferroelectric hysteresis loop characteristic collection of illustrative plates after embodiment under an increased pressure various dose irradiation.
Specific embodiment
In order to allow those skilled in the art to more fully understand technical scheme, below in conjunction with the accompanying drawings to the present invention It is further elaborated.
Highly anti-radiation ferroelectricity HfO with yttrium content as 3.8mol.%2Film is embodiment to the specific steps in the present invention It is described in detail：
Step 1：Using magnetron sputtered deposition technology, in SiO2One layer of TiAlN thin film of 100nm is deposited in/Si substrates first As hearth electrode.
Wherein, step 1 is specially：Take SiO2/ Si substrates, its surface is cleaned with organic solvent and deionized water, is removed Impurity.Organic solvent includes acetone and ethanol.In silicon chip dipping and acetone, ethanol, deionized water, will be placed in successively ultrasonic clear It is cleaned by ultrasonic in clean instrument each 3 minutes, and is dried up with nitrogen immediately.
A, by the SiO after cleaning2/ Si substrates are placed in target top in vacuum chamber, and target-substrate distance is fixed as 55mm, substrate temperature It is increased to 300 DEG C；
B, 99.999% argon gas is passed through, control pressure starts depositing TiN hearth electrode after 0.13Pa, pre-sputtering 5min；
After c, growth terminate, sample is down to room temperature under vacuum, is taken out from vacuum chamber.
Step 2：Using pulsed laser deposition PLD technologies, 20nm doped yttriums are grown in the TiAlN thin film that step 1 is obtained HfO2Film.Specially：
A, the sample taken out in step 1 is placed in vacuum chamber target top, target-substrate distance is fixed as 55mm, substrate temperature liter Up to 100 DEG C；
B, 99.999% oxygen is passed through, control oxygen is pressed in 1Pa, uses laser (KrF) ablation rotation that wavelength is 248nm Target material surface, laser energy is 2.5J/cm2, carry out HfO2Target and yittrium oxide target are exchanged practices shooting, wherein laser hits HfO2 The pulse frequency of target is 5Hz, under strike 36；The pulse frequency for hitting yittrium oxide target is 2Hz, under strike 1.So circulation 28 Time, thickness is obtained for 20nm, yttrium content is the amorphous HfO of 3.8mol.%2Film.
Step 3：Using PLD technologies, the HfO of yttrium is mixed in amorphous obtained in step 22The TiN of growth in situ 30nm on film Top electrode.Specially：
A, step 2 terminate after, stopping be passed through oxygen, make cavity keep high vacuum state, by substrate temperature in 5 minutes by 100 DEG C at the uniform velocity rise to 200 DEG C；
B, 99.999% argon gas is passed through, air pressure is maintained at 0.5Pa, uses laser (KrF) ablation that wavelength is 248nm to rotate Nitridation titanium target material surface, laser energy is 4J/cm2, laser pulse frequency is 10Hz, grows the TiN top electrodes of 30nm；
After c, growth terminate, sample drops to room temperature in high vacuum condition natural cooling, is taken out from vacuum chamber.
Step 4：Using short annealing RTA technologies, the sample obtained to step 3 carries out short annealing treatment, obtains polycrystalline The HfO for mixing yttrium2Ferroelectric thin film.Specially：
A, by step 3 take out sample be placed in quick anneal oven, be passed through 99.999% nitrogen, air pressure is maintained at 2mTorr, 30s are warming up to 600 DEG C, are incubated 1 minute, naturally cool to room temperature.Sample is taken out, is obtained with ferroelectric polycrystalline HfO2Film.
To HfO obtained in embodiment2Ferroelectric material carries out irradiation test, and the irradiation bomb for being used is γ-Co60：
Obtained HfO2XRD test result of the ferroelectric material after different irradiation doses is as shown in Figure 2.Can be with from Fig. 2 Find out, obtained HfO2There is no obvious change after irradiated by 10.8Mrad accumulated doses in ferroelectric material structure Change, crystalline phase is still stablized with ferroelectric orthorhombic phase, does not have new dephasign to generate.Illustrate that the material has the anti-spoke of stabilization According to performance.
Obtained HfO2I-V characteristic test result of the ferroelectric material after different irradiation doses is as shown in Figure 3.From Fig. 3 As can be seen that there is no obvious change after irradiated by 11.88Mrad accumulated doses in the leakage current of the material, with Predose is basically identical.
HfO obtained in embodiment2C-V characteristic test result of the ferroelectric material after different irradiation doses is as shown in Figure 4.From In Fig. 4 as can be seen that the dielectric constant of the material do not occur after irradiated by 10.8Mrad accumulated doses it is obvious Change, it is basically identical with predose.
HfO obtained in embodiment2Ferroelectric hysteresis loop characteristic test result such as Fig. 5 institute of the ferroelectric material after different irradiation doses Show.From figure 5 it can be seen that the ferroelectric hysteresis loop of the material does not occur after irradiated by 12.96Mrad accumulated doses Obvious change, it is basically identical with predose.Ferroelectric hysteresis loop is often under so total dose irradiation high for traditional ferroelectric material Can deform, so as to cause component failure.Therefore compare with traditional material, HfO2Ferroelectric material has high Flouride-resistani acid phesphatase Energy.
HfO obtained in embodiment2Fatigue properties test result of the ferroelectric material after different irradiation doses such as Fig. 6-Fig. 9 institutes Show.The field intensity that fatigue properties are tested in Fig. 6-Fig. 9 is respectively 1.3MV/cm, 1.4MV/cm, 1.6MV/cm, 1.8MV/cm.From figure 6- Fig. 9 can be seen that fatigue properties of the material after irradiated by 10.8Mrad accumulated doses under different field intensity are relatively irradiated It is preceding that significant change does not occur, or even slightly improve.This explanation HfO2Ferroelectric material is maintained in the environment of irradiation The primary characteristic of material, will not be influenceed by irradiating, and this is significant for the stability of device.
HfO obtained in embodiment2Ferroelectric material ferroelectric hysteresis loop characteristic test under an increased pressure after different irradiation doses Result is as shown in Figure 10.Even it can be seen from fig. 10 that in the case of pressurizeing at the same time and irradiating, the electric hysteresis of the material is returned There is no obvious change in line, basically identical with predose after irradiated by 1.26Mrad accumulated doses.Explanation HfO2Ferroelectric material still has good anti-radiation performance in the environment of irradiation of pressurizeing.
Be may certify that by above-mentioned test, HfO2Ferroelectric material has highly anti-radiation performance, can be with radiation environment Ensure that device normally runs for a long time.Therefore HfO2It is such that ferroelectric material can operate with nuclear industry, space flight and core hospitality industry The extreme operating environments of radiation environment high.

Claims (3)

1. a kind of HfO2The application method of base ferroelectric material, it is characterised in that：It is applied to extreme operating environments.
2. HfO as claimed in claim 12The application method of base ferroelectric material, it is characterised in that：The extreme operating environments are height Radiation environment.
3. HfO as claimed in claim 22The application method of base ferroelectric material, it is characterised in that：The radiation environment high is core work Industry, space flight and core hospitality industry.
CN201611033497.2A 2016-11-23 2016-11-23 A kind of HfO2The application method of base ferroelectric material Pending CN106783531A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109100900A (en) * 2018-07-23 2018-12-28 电子科技大学 A kind of HfO2The application method of base ferroelectric material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090263972A1 (en) * 2008-04-04 2009-10-22 Applied Materials, Inc. Boron nitride and boron-nitride derived materials deposition method
CN102282673A (en) * 2008-11-13 2011-12-14 韩国科学技术院 Transparent memory for transparent electronic device
CN105788864A (en) * 2016-02-29 2016-07-20 湘潭大学 Method for improving negative capacitance of PZT ferroelectric thin film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090263972A1 (en) * 2008-04-04 2009-10-22 Applied Materials, Inc. Boron nitride and boron-nitride derived materials deposition method
CN102282673A (en) * 2008-11-13 2011-12-14 韩国科学技术院 Transparent memory for transparent electronic device
CN105788864A (en) * 2016-02-29 2016-07-20 湘潭大学 Method for improving negative capacitance of PZT ferroelectric thin film

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109100900A (en) * 2018-07-23 2018-12-28 电子科技大学 A kind of HfO2The application method of base ferroelectric material
CN109100900B (en) * 2018-07-23 2020-11-17 电子科技大学 Application method of HfO 2-based ferroelectric material

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Application publication date: 20170531