WO2010016130A1 - Support pour mémoire d’enregistrement / de reproduction d’informations et procédé pour sa fabrication - Google Patents

Support pour mémoire d’enregistrement / de reproduction d’informations et procédé pour sa fabrication Download PDF

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Publication number
WO2010016130A1
WO2010016130A1 PCT/JP2008/064221 JP2008064221W WO2010016130A1 WO 2010016130 A1 WO2010016130 A1 WO 2010016130A1 JP 2008064221 W JP2008064221 W JP 2008064221W WO 2010016130 A1 WO2010016130 A1 WO 2010016130A1
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Prior art keywords
layer
recording
memory medium
information recording
reproducing memory
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PCT/JP2008/064221
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English (en)
Japanese (ja)
Inventor
篤 尾上
健二郎 藤本
高博 河野
昌樹 楠原
優 梅田
昌之 都田
正裕 田村
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パイオニア株式会社
株式会社ワコム研究所
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Priority to JP2010523689A priority Critical patent/JP5427991B2/ja
Priority to PCT/JP2008/064221 priority patent/WO2010016130A1/fr
Publication of WO2010016130A1 publication Critical patent/WO2010016130A1/fr

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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B9/00—Recording or reproducing using a method not covered by one of the main groups G11B3/00 - G11B7/00; Record carriers therefor
    • G11B9/02—Recording or reproducing using a method not covered by one of the main groups G11B3/00 - G11B7/00; Record carriers therefor using ferroelectric record carriers; Record carriers therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B9/00—Recording or reproducing using a method not covered by one of the main groups G11B3/00 - G11B7/00; Record carriers therefor
    • G11B9/12—Recording or reproducing using a method not covered by one of the main groups G11B3/00 - G11B7/00; Record carriers therefor using near-field interactions; Record carriers therefor
    • G11B9/14—Recording or reproducing using a method not covered by one of the main groups G11B3/00 - G11B7/00; Record carriers therefor using near-field interactions; Record carriers therefor using microscopic probe means, i.e. recording or reproducing by means directly associated with the tip of a microscopic electrical probe as used in Scanning Tunneling Microscopy [STM] or Atomic Force Microscopy [AFM] for inducing physical or electrical perturbations in a recording medium; Record carriers or media specially adapted for such transducing of information
    • G11B9/1463—Record carriers for recording or reproduction involving the use of microscopic probe means
    • G11B9/149—Record carriers for recording or reproduction involving the use of microscopic probe means characterised by the memorising material or structure

Definitions

  • the present invention relates to an information recording / reproducing memory medium and a manufacturing method thereof.
  • Such high-density recording technology capable of random access includes magnetic recording, optical recording, and semiconductor memory.
  • information and communication technology has been remarkably developed, the capacity of information has been increased, and higher density and larger capacity recording has been demanded.
  • higher density and larger capacity recording has been demanded.
  • Ferroelectric memories are considered capable of higher density recording, and are expected as next-generation high-density recording systems.
  • Probe memory technology that utilizes the principle of a scanning probe microscope is expected as a recording method that improves recording density.
  • This includes a recording medium, an actuator that is installed on the stage and is driven in the XY direction, and a micro probe (probe chip) for executing information writing to or reading from the recording medium.
  • a signal processing unit that appropriately processes this information and outputs desired data.
  • Information is read or written by approaching or contacting a probe chip with a desired position on a recording medium (also referred to as a recording medium) and detecting various physical quantities on the recording medium with a spatial resolution at the atomic and molecular level. Accordingly, there is a need for a highly accurate XY actuator that can perform driving of two or more axes in the XY direction. Further, in the Z-axis direction, a probing drive unit that deforms the probe in synchronization with the recording media moving on the XY plane and brings the probe tip closer to or in contact with the recording medium is required.
  • an SNDM ferroelectric probe memory 10 has been developed by the present inventor as shown in FIG.
  • SNDM scanning nonlinear dielectric microscope
  • the ferroelectric recording medium 21 has a layer structure in which an electrode layer 23 and a ferroelectric layer 24 are sequentially formed on an upper layer of a substrate 22.
  • An example of the appearance of the ferroelectric recording medium 21 is shown in FIG.
  • ensuring in-plane uniformity on the medium surface is important for improving reliability (for example, suppression of errors and data loss) and yield.
  • the ferroelectric probe memory does not require an upper electrode in the upper layer of the ferroelectric layer 24 unlike the FeRAM and the like, and the probe (head) 11 replaces the electrode. It has become. That is, the ferroelectric memory does not require an upper electrode.
  • the surface of the ferroelectric layer 24 of the recording media is an exposed surface.
  • FeRAM FeRAM
  • one capacitor is formed for each bit, or a transistor using a ferroelectric as a gate insulating film is formed.
  • the Z-axis component of the polarization of the ferroelectric layer is used for recording. Therefore, a ferroelectric film having a C-axis orientation is preferable.
  • the ferroelectric layer is formed as follows. (1) Chromium (Cr) is deposited as a lower electrode on a LiTaO 3 (CLT) single crystal (3 inch diameter, 500 ⁇ m). (2) The CLT wafer on which chromium is vapor-deposited is attached to the Si substrate or the CLT substrate. (3) The CLT wafer is polished to a thickness of about 1 ⁇ m by mechanical polishing. (4) Finish to a thickness of about 50 nm by dry etching with a mixed gas of Ar and O 2 . The reason why the crystal thickness is thinned to 100 nm or less is to achieve low voltage driving, high speed, and high density recording.
  • Chromium (Cr) is deposited as a lower electrode on a LiTaO 3 (CLT) single crystal (3 inch diameter, 500 ⁇ m).
  • the CLT wafer on which chromium is vapor-deposited is attached to the Si substrate or the CLT substrate.
  • the CLT wafer is polished to a thickness of about 1 ⁇ m by
  • Non-Patent Document 1 This technique enables high-density recording exceeding 1T (terra) bit / inch 2 .
  • Non-Patent Document 1 since a wafer is used as a starting material as the ferroelectric layer, a large amount of polishing must be performed.
  • the ferroelectric recording layer may be made of a Pb-based material such as Pb (Zr, Ti) O 3 [PZT] exhibiting excellent ferroelectricity, SrBi 2 Ta 2 O 9 [SBT] or Bi. 4 Ti 3 O 12 [BIT] or the like is used, and among these, Pb (Zr, Ti) O 3 [PZT] is preferable because it has a large residual polarization.
  • Pb (Zr, Ti) O 3 [PZT] exhibiting excellent ferroelectricity, SrBi 2 Ta 2 O 9 [SBT] or Bi. 4 Ti 3 O 12 [BIT] or the like is used, and among these, Pb (Zr, Ti) O 3 [PZT] is preferable because it has a large residual polarization.
  • a feature of the ferroelectric is that it has spontaneous polarization, and its direction can be controlled by an electric field. By using two stable points with respect to the direction of the electric field, “0” “ 1 "and can be recorded by switching between them at high speed.
  • recording / erasing of information with respect to such a semiconductor memory or the like is performed by, for example, a recording / erasing apparatus having an atomic force microscope (AFM) configuration, and a recording head by a conductive cantilever having the needle electrode is brought into contact with the semiconductor memory.
  • AFM atomic force microscope
  • High-speed recording is possible by applying a high-speed pulse voltage of 20 V or less from the recording head, that is, a conductive cantilever, and reversing the direction of spontaneous polarization of the ferroelectric recording layer locally and at high speed.
  • each constituent layer such as an electrode layer and a ferroelectric recording layer may be formed by, for example, sputtering, MOCVD (Metal Organic Chemical Deposition), LPCVD (low pressure CVD), molecular beam deposition, normal deposition,
  • the film can be formed by a MOD (Metal Oxide Deposition) method, a laser ablation method, a sol-gel method, a spin coating method, a thermal oxidation method, a thermal nitridation method, or the like.
  • an object of the present invention is to provide an information recording / reproducing memory medium capable of ensuring stable recording / reproduction by realizing local averaging of recording layers.
  • an information recording / reproducing memory medium is as follows.
  • the composition according to the first aspect of the present invention is such that the composition in the particles in the granular particles straddling the electrode layer to the recording layer changes in a gradient manner.
  • continuous columnar particles can be formed in the electrode layer and the recording layer, and a conductive portion (conductive portion) is formed. Therefore, charge-up can be suppressed and the crystallinity can be kept high.
  • an information recording / reproducing memory medium in which one electrode layer and a recording layer are laminated in this order on a substrate, and at least one kind of atoms constituting the composition of the electrode layer or the recording layer.
  • An information recording / reproducing memory medium characterized in that the density changes in an inclined manner.
  • the atomic concentration when the atomic concentration is changed in an inclined manner, continuous particles (particularly columnar particles) extending between the electrode layer and the recording layer are formed. This particle becomes a conductive part.
  • the conductivity also changes in an inclined manner.
  • the invention according to claim 3 is an information recording / reproducing memory medium having at least a three-layer structure in which an electrode layer and a recording layer are stacked on a substrate, wherein the electrode layer and the recording layer have the same crystal structure.
  • An information recording / reproducing memory medium characterized by comprising:
  • the recording layer can be grown with a good crystal structure from the initial stage of growth.
  • the invention according to claim 4 is the information recording / reproducing memory medium according to any one of claims 1 to 3, wherein the information recording / reproducing memory medium is a probe memory medium.
  • a head or a probe In a probe memory medium, a head or a probe relatively scans the medium to record and reproduce information. That is, in the probe memory medium, there is no upper electrode on the upper surface of the memory medium, and it is exposed. In such a state, the effect of preventing the medium surface from being charged up due to the presence of the conductive portion in the recording layer is particularly effective.
  • the probe is not particularly limited as long as information can be written to or read from the recording layer, and may be referred to as a probe or a probe tip.
  • the invention according to claim 5 is the information recording according to claim 3 or 4, wherein the atomic concentration of at least one of the atoms constituting the composition of the electrode layer or the recording layer changes in a gradient manner.
  • a playback memory medium is the information recording according to claim 3 or 4, wherein the atomic concentration of at least one of the atoms constituting the composition of the electrode layer or the recording layer changes in a gradient manner.
  • continuous columnar particles can be formed in the electrode layer and the recording layer, charge-up can be suppressed, and high crystallinity can be maintained.
  • the invention according to claim 6 is the information recording according to any one of claims 1, 2, 4, and 5, wherein the atomic concentration changes in an inclined manner over both the electrode layer and the recording layer.
  • a playback memory medium The gradient change of the atomic concentration may exist only in each of the electrode layer or the recording layer, but the fact that the gradient changes across both the electrode layer and the recording layer is an effect of the invention. Is even more effective.
  • the invention according to claim 7 is the information recording / reproducing memory medium according to any one of claims 1, 2, and 4 to 6, wherein atoms of the electrode layer and the recording layer are diffused. . It is particularly preferable that atoms in the electrode layer and the recording layer are diffused from each other.
  • the conductive portion can be formed by diffusion.
  • the structure of the atoms of the electrode layer and the recording layer, the composition of which is easily changed in a gradient, can be realized.
  • the invention according to claim 8 is the information recording / reproducing memory medium according to any one of claims 1 to 7, wherein the recording layer is a ferroelectric recording layer.
  • the recording layer is made of Pb (Zr, Ti) O 3 [PZT], SrBi 2 Ta 2 O 9 (SBT), Bi 4 Ti 3 O 12 (BIT), LiTaO 3 , LiNbO 3 .
  • PZT Pb (Zr, Ti) O 3 [PZT]
  • SBT SrBi 2 Ta 2 O 9
  • BIT Bi 4 Ti 3 O 12
  • LiTaO 3 LiNbO 3
  • the invention according to claim 10 is the information recording / reproducing memory medium according to claim 9, wherein the recording layer has a higher proportion of the Pb raw material as it goes to the upper layer than the lower layer.
  • the invention according to claim 11 is the information recording / reproducing memory medium according to claim 9, wherein the ratio of the upper layer portion of the Pb material of the recording layer is in the range of 20% to 22% (atomic%). is there.
  • the invention according to claim 12 is characterized in that the crystal grain diameter of the electrode layer and the recording layer is the same as or smaller than the recording pit diameter.
  • one bit is composed of a plurality of particles, and the characteristic signal of each bit can be averaged.
  • the invention according to claim 13 is the information recording / reproducing memory medium according to claim 12, wherein the crystal grain size of the electrode layer is a crystal having a grain size smaller than the crystal grain size of the recording layer. .
  • the recording layer can grow following the underlying particles, and a recording layer having small particles can be grown.
  • the invention according to claim 14 is the information recording / reproducing memory medium according to any one of claims 1 to 13, wherein the electrode layer is formed of a film having no orientation.
  • the invention according to claim 15 is the information recording / reproducing memory medium according to any one of claims 1 to 11, wherein the recording layer is formed of a film having no orientation.
  • the recording layer having small particles can be obtained by making the lower layer further smaller than the target particle diameter of the recording layer. Can be grown, and the upper layer can also be non-oriented because the lower layer is non-oriented.
  • the invention according to claim 16 is the information recording / reproducing memory medium according to any one of claims 1 to 15, wherein the electrode layer is a conductive oxide.
  • the invention according to claim 17 is the information recording / reproducing memory medium according to claim 15, wherein the element of the electrode layer is any one of SRO, LSCO, LaNiO 3 , and Nb-STO.
  • the electrode is made of an oxide. Therefore, a recording layer with good crystallinity can be grown.
  • the constituent atoms of the recording layer for example, PZT
  • the electrode is made of an oxide
  • the function as an electrode is not impaired by the influence of oxygen in the recording layer material.
  • the electrode layer is made of an oxide, a recording layer having excellent crystallinity without voids can be grown. In addition, adhesion to the substrate side can be improved.
  • the invention according to claim 18 is the information recording / reproducing memory medium according to any one of claims 1 to 17, wherein an amorphous layer is interposed between the substrate and the front electrode layer. Since the amorphous layer is formed between the substrate and the electrode layer, atoms of the material constituting the electrode can be prevented from diffusing into the substrate (for example, a silicon substrate).
  • the amorphous layer can be formed, for example, by heating the surface of the substrate in an oxidizing atmosphere and growing a thermal oxide film. For example, when the substrate is silicon, SiO 2 may be formed.
  • the thickness of the amorphous layer is preferably 50 nm or more. By setting it to 50 nm or more, diffusion to the substrate can be reliably prevented. In addition, from a viewpoint of size reduction, 700 nm or less is preferable and 500 nm or less is more preferable.
  • the ferroelectric layer includes a conductive portion.
  • a recording / reproducing memory medium in which an electrode layer and a ferroelectric recording layer are laminated on a substrate, the ferroelectric layer includes a conductive portion.
  • the conductive part can be formed by changing the composition of the particles in the granular particles straddling the ferroelectric layer from the electrode layer in an inclined manner. Further, it can be formed by changing the concentration of at least one of atoms constituting the composition of the electrode layer or the dielectric layer in an inclined manner.
  • the conductive portion and the insulating portion may be separated.
  • the conductive material may be introduced in a mesh form. Continuous columnar particles can be formed in the electrode layer and the recording layer, charge-up can be suppressed, and high crystallinity can be maintained.
  • the nineteenth aspect of the present invention it is possible to avoid the problem that the surface charge tends to be excessive or insufficient when the polarization of the ferroelectric layer is reversed.
  • the invention according to claim 20 is the information recording / reproducing memory medium according to claim 19, wherein the information recording / reproducing memory medium is a probe memory medium. According to the present invention, the same effect as described in claim 4 can be obtained.
  • the invention according to claim 21 is the information recording / reproducing memory medium according to any one of claims 1 to 20, wherein the uppermost layer portion is formed of an amorphous layer.
  • the chemical change of the upper layer portion of the substrate can be suppressed.
  • the invention according to claim 22 is characterized in that a protective layer is provided above the recording layer, and the protective layer has a particle size smaller than that of the recording layer or an amorphous layer.
  • Item 22 The information recording / reproducing memory medium according to any one of Item 21.
  • the invention according to claim 23 is the information recording / reproducing memory medium according to claim 22, wherein the protective layer includes all of the constituent atoms of the previous recording layer.
  • the surface protection performance can be improved.
  • the invention according to claim 24 is the information recording / reproducing memory medium according to claim 23, wherein the composition ratio between the protective layer and the recording layer is the same.
  • the twenty-fourth aspect of the present invention it is possible to mitigate changes in characteristics when the protective layer is crystallized or the recording layer is decomposed by an electric field, pressure, heat or the like from a probe head or the like.
  • the protective layer is a layer obtained by chemically polishing the surface of the recording layer. It is a medium.
  • the invention according to claim 26 is the information recording / reproducing memory medium according to any one of claims 22 to 25, wherein the surface of the protective layer is plasma-etched.
  • the protective layer can be easily manufactured.
  • the twenty-seventh aspect of the invention it is possible to mitigate the influence of the recording layer particle shape and the grain boundary on the reproduction signal.
  • the invention according to claim 28 is the information recording / reproducing memory medium according to claim 27, wherein a lubricating layer is laminated on the protective layer or the surface layer.
  • the invention according to claim 29 is an electrode layer forming step of forming an electrode layer on a substrate; A recording layer forming step of forming a recording layer on the electrode layer; Electrode for diffusing atoms in the electrode layer into the recording layer-recording layer diffusion step, Recording-electrode layer diffusing step for diffusing atoms in the recording layer into the electrode layer, atoms in the electrode layer A method for producing an information recording / reproducing memory medium, comprising: an interdiffusion step of diffusing into a recording layer and diffusing atoms in the recording layer into the electrode layer.
  • the recording layer can be grown with a good crystal structure from the initial stage of growth.
  • a structure with an inclined composition can be easily produced.
  • the invention according to claim 30 is the method of manufacturing an information recording / reproducing memory medium according to claim 29, wherein the information recording / reproducing memory is a probe memory. According to the invention of claim 30, the same effect as that of the invention of claim 4 is obtained.
  • the invention according to claim 31 is characterized in that, after executing any one of the respective diffusion steps, one or both of a CMP processing step for performing chemical mechanical polishing processing and an etching processing step for performing plasma etching are performed.
  • the invention according to Claim 32 includes the step of forming an amorphous layer between the substrate and the electrode layer, and a method of manufacturing an information recording / reproducing memory medium according to any one of Claims 29 to 32 It is. The effect similar to that of the invention of the nineteenth aspect is achieved.
  • the invention according to claim 33 is the method of manufacturing an information recording / reproducing memory medium according to any one of claims 29 to 32, wherein in each diffusion step, atoms are diffused by heat treatment.
  • the invention according to claim 34 is the method of manufacturing an information recording / reproducing memory medium according to claim 32 or 33, wherein the substrate is silicon and the amorphous layer is a silicon oxide film.
  • a thirty-fifth aspect of the present invention is the information recording / reproducing memory medium manufacturing method according to any one of the thirty-second to thirty-fourth aspects, wherein the amorphous layer is 50 nm or more.
  • a thirty-sixth aspect of the invention is the information recording / reproducing memory medium manufacturing method according to any one of the twenty-ninth to thirty-fifth aspects, wherein the electrode layer is made of an SRO film, and the recording layer is made of a PZT film.
  • the thirty-sixth aspect of the present invention it is possible to form a non-oriented layer of fine particles with good crystallinity following the SRO in the PZT film forming step.
  • the material ratio of PZT is Pb 1.1 (Zr 0.4 , Ti 0.6 ) O 3 , mutual diffusion of Pb and Sr during post-annealing is promoted and sputtering gas is used.
  • Ar + O 2 since it is an oxide electrode, it is possible not only to prevent oxygen deficiency of the film by introducing O 2 gas, but also to have the same perovskite structure as PZT, and good crystallinity immediately after deposition (lowermost layer of PZT). Can be obtained.
  • the deposited electrode layer becomes non-oriented, the volume resistivity can be about 5 ⁇ 10 ⁇ 4 , and the thickness can be about 50 nm, and a fine particle film, that is, PZT of fine particles can be grown thereon.
  • the invention according to claim 37 is the method of manufacturing an information recording / reproducing memory medium according to any one of claims 29 to 36, wherein the recording layer is formed by MOCVD film formation.
  • a thirty-eighth aspect of the invention is the information recording / reproducing memory medium manufacturing method according to any one of the thirty-third to thirty-seventh aspects, wherein the heat treatment is performed at 500 to 700 ° C.
  • the invention according to claim 39 is characterized in that the content of atoms diffusing in each layer of the electrode layer and the recording layer before the diffusion step is larger than the stoichiometric ratio.
  • the recording layer can be stabilized as a result by realizing local averaging of the recording layer.
  • Ferroelectric material retains information (polarization) even if it is conductive. When there is conductivity, both electrodes are always short-circuited as a capacitance. In the ferroelectric probe memory, reading is possible even if neutralization is performed. In the ferroelectric probe memory, the surface of the ferroelectric layer is exposed without an upper electrode. Therefore, if the ferroelectric layer has conductivity, it is possible to prevent the medium surface from being charged up.
  • 1 is a substrate (Si substrate, glass substrate, aluminum substrate), 2 is an electrode layer provided on the upper layer of the substrate 1, 3 is a ferroelectric recording layer provided on the upper layer of the electrode layer 2, 4 is a protective layer, 5 Is a surface layer, and 6 is a lubricating layer.
  • FIG. 1 is a sectional view of an information recording / reproducing memory medium of the present invention.
  • 1 is a substrate (Si substrate, glass substrate, aluminum substrate), 2 is an electrode layer provided in the upper layer of the substrate 1, 3 is a ferroelectric recording layer provided in the upper layer of the electrode layer 2, and 4 is A protective layer, 5 is a surface layer, and 6 is a lubricating layer.
  • a ferroelectric recording layer 3 of Pb (Zr, Ti) O 3 [PZT] is formed (deposited) on the electrode layer 2 by MOCVD.
  • Si wafer thermal oxidation step S1
  • SRO electrode sputtering step S2
  • PZT film formation step S3
  • RTA post-annealing
  • CMP step S5
  • plasma etching step S6
  • step S1 50 nm or more is preferable for the purpose of preventing the electrode material from diffusing into Si.
  • the upper limit is preferably 700 nm.
  • the SRO film is formed by sputtering at a high temperature (500 ° C. or higher), so that a good film formation cannot be obtained by the current post-annealing, and problems such as morphology can be solved. it can.
  • the electrode layer 2 preferably has the same crystal structure (perovskite structure in this example) as that of the ferroelectric recording layer (PZT layer in this example) 3.
  • the difference in the lattice constant of the crystal of the material constituting the electrode layer 2 and the ferroelectric recording layer 3 is preferably within 4%, and particularly the difference in the lattice constant is preferably within 2%.
  • the crystal grains of the ferroelectric recording layer 3 grow along the crystal grains of the electrode layer 2, and are excellent crystals with few dislocations and vacancies immediately after deposition (the lowest layer of the PZT) and with little intragranular distortion. It is formed as a layer having properties.
  • the film surface is preferably sputter etched. Generally, a power of about 100 W is used during film formation, but the film surface is damaged. Therefore, it is preferable to remove the damaged layer by performing sputter etching with low power (for example, 40 W or less).
  • the formed SRO becomes non-oriented
  • the volume resistivity can be about 5 ⁇ 10 ⁇ 4
  • the thickness can be about 50 nm
  • a fine particle film, that is, fine PZT can be grown.
  • step S3 for example, the film formation is performed using MOCVD, and the set temperature at that time is set to 500 ° C. or less, and the crystallinity at this time is poor (for example, XRD inspection result) PZT.
  • adding a little more Pb Pb 1.1 (Zr 0.4 , Ti 0.6 ) O 3 ) promotes the mutual diffusion of Pb and Sr during post-annealing and imitates SRO.
  • a non-oriented layer with fine particles can be obtained.
  • the particles grow (thickness 50 nm to 200 nm) toward the upper layer, it is desirable to set the particle diameter of the underlayer in consideration of the upper layer particle growth.
  • the recording layer is formed by sputtering, it is extremely difficult to control the composition of the composition component (for example, Pb) of the recording layer, and a recording layer having a desired composition cannot always be obtained.
  • the composition component for example, Pb
  • MOCVD Metal Organic Chemical Vapor Deposition
  • step S4 the post-annealing (RTA) (step S4), PZT crystallization annealing (recovery annealing) as rapidly heated in an O 2 atmosphere (heating rate of about 100K / s, temperature of 500 °C ⁇ 700 °C (PZT deposition temperature of the Higher temperature) and holding time of 30 sec to 5 min), crystallization or crystallinity can be improved and ferroelectricity can be exhibited.
  • Pb, Sr mutual diffusion occurs, and the recording layer is somewhat It becomes conductive and can suppress excess and deficiency of electric charge, and can have characteristics suitable for recording.
  • step S4 the surface roughened by the physical, chemical, and thermal actions after each of the above steps is planarized. At this time, the polishing is performed to a target thickness (20 nm to 150 nm).
  • step S5 plasma etching (step S5) is performed to remove the above-mentioned damaged layer by CMP by etching with 0 to 5 nm using Ar + O 2 plasma.
  • Electrode layer 2 is not particularly limited and may be appropriately selected depending on the purpose.
  • the electrode layer 2 can be formed on the substrate 1 (1a) by a sputtering method or the like.
  • the conditions for forming the electrode layer 2 by sputtering or the like are not particularly limited and can be appropriately selected depending on the purpose.
  • a material having the same crystal structure can be appropriately selected according to the purpose depending on the material of the ferroelectric recording layer 3, for example, SRO, LSCO, LaNiO 3 , Nb— STO (Nb-doped STO) or the like is suitable, and among these, when PZT is used for the ferroelectric recording layer 3, it is preferable to use SRO from the viewpoint of promoting Pb diffusion. Since SRO and PZT have the same crystal structure, it is considered that interdiffusion of Pb and Sr is likely to occur. However, even when compared with other combinations having the same crystal structure, mutual diffusion tends to occur in the combination of SRO and PZT. Further, by making the electrode layer non-oriented, the recording layer can also be made non-oriented.
  • the thickness of the electrode layer 2 is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is about 10 to 1000 nm, and preferably 50 to 500 nm.
  • the amorphous layer 1a in the upper layer portion of the substrate 1, for example, the diffusion when the above-described conductive oxide is used as the material of the electrode layer 2 is prevented. Not limited to various materials reacting with Si, the adhesion to the amorphous layer 1a is improved.
  • the ferroelectric recording layer 3 is formed at a temperature equal to or higher than the crystallization temperature that takes a crystallization structure exhibiting ferroelectricity.
  • the crystallization temperature at which the crystallization structure exhibiting ferroelectricity varies depending on the material of the ferroelectric, but generally, when the ferroelectric recording layer 3 is Pb (Zr, Ti) O 3 [PZT] Is preferably 500 ° C. or higher, more preferably 500 to 700 ° C.
  • the crystallized structure exhibiting ferroelectricity means, for example, a perovskite crystal structure.
  • the ferroelectric recording layer 3 preferably has a perovskite crystal structure.
  • the ferroelectric recording layer 3 preferably has a columnar structure in that high-density and high-strength crystals can be obtained.
  • Perovskite crystal structure wherein represented by ABX 3.
  • the cation (cation) at the A site and the anion (anion) at the X site have the same size, and in the cubic unit cell composed of the A site and the X site.
  • cations smaller in size than the A site are located at the B site.
  • the ferroelectric material for forming the ferroelectric recording layer 3 can be appropriately selected according to the purpose.
  • Pb (Zr, Ti) O 3 [PZT] SrBi 2 Ta 2 O 9 ( SBT), Bi 4 Ti 3 O 12 (BIT), LiTaO 3 , LiNbO 3 , and the like. These may be used individually by 1 type and may use 2 or more types together. At this time, among these, Pb (Zr, Ti) O 3 [PZT] is preferable in that the remanent polarization is large.
  • the ferroelectric recording layer 3 is formed of, for example, Pb (Zr x , Ti 1-x ) O 3 [PZT] converted from an amorphous structure to a perovskite crystal structure. Yes.
  • a method for forming the ferroelectric recording layer 3 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a chemical solution deposition (CSD) method, a metal organic chemical vapor deposition ( It can be formed by a method selected from a metalorganic chemical vapor deposition (MOCVD) method, a pulse laser deposition (pulse laser deposition; PLD) method, a sol-gel method, a sputtering method, etc. Among them, the step coverage is good.
  • the MOCVD method is preferable because high-density ferroelectric crystals can be obtained.
  • the MOCVD method is excellent in composition controllability, and it is possible to accurately realize the amount of the component that is larger than the stoichiometric ratio diffused by heat treatment (RTA).
  • RTA heat treatment
  • epitaxial growth from the electrode layer is an important factor, but the MOCVD method is particularly preferable because excellent epitaxial growth can be realized.
  • the raw material gas, reaction conditions, and the like when forming the ferroelectric recording layer 3 by the MOCVD method differ depending on the type of the ferroelectric recording layer 3 to be formed and cannot be defined unconditionally.
  • 3 is Pb (Zr x Ti 1-x ) O 3 [PZT]
  • a Pb raw material, a Zr raw material, a Ti raw material, or the like is used as the raw material.
  • Examples of the Pb raw material include Pb (DPM) 2 and the like.
  • Examples of the Zr raw material include Zr (dmhd) 4 .
  • Examples of the Ti raw material include Ti (O—iPr) 2 (DPM) 2 and the like.
  • the flow rate of the Pb raw material is about 0.01 to 1.0 ml / min, preferably 0.1 to 0.5 ml / min, and the flow rate of the Zr raw material is about 0.01 to 1.0 ml / min.
  • the flow rate of the Ti raw material is about 0.01 to 1.0 ml / min, preferably 0.1 to 0.5 ml / min.
  • the oxygen partial pressure in the raw material gas after vaporization is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is about 1 to 10 Torr (133 to 1333 Pa), and is 3 to 7 Torr (399 to 933 Pa). ) Is preferred.
  • the raw material preparation method is not particularly limited and can be appropriately selected depending on the purpose.
  • the solution is publicly known.
  • the method of vaporizing using a vaporizer is mentioned.
  • the vaporized source gas is, for example, mixed with oxygen gas and adjusted to a predetermined oxygen gas partial pressure, and then sprayed onto the upper layer of the electrode layer 2 using a shower head or the like, thereby A ferroelectric recording layer 3 can be formed on the layer 2.
  • the reaction conditions are not particularly limited and can be appropriately selected according to the purpose.
  • the temperature differs depending on the type of the ferroelectric recording layer 3 to be formed and cannot be defined unconditionally.
  • the temperature is usually about 580 to 620 ° C.
  • the MOCVD film is deposited in a low crystallinity state at 500 ° C. or lower and crystallized by RTA (580 ° C.) in the subsequent process.
  • the deposition temperature of Pb (Zr x , Ti 1-x ) O 3 [PZT] can be 600 ° C. or lower, and further 500 ° C. or lower (for example, 475 ° C.).
  • Pb (DPM) 2 is 0.05 to 0.5 ml / min as a Pb raw material
  • Zr (dmhd) 4 is 0.01 to 0.10 ml / min as a Zr raw material
  • Ti (O—iPr) 2 is a Ti raw material.
  • (DPM) 2 is introduced at 0.05 to 0.3 ml / min.
  • the crystal grains of Pb (Zr x , Ti 1-x ) O 3 [PZT] constituting the ferroelectric recording layer 3 have the same crystal structure but different components and compositions.
  • the crystal layer is microcrystalline (for example, 30 nm or less).
  • microcrystal means that the grain size is about the same as or smaller than the recording pit diameter (for example, 30 nm), and one bit is composed of one or more microcrystals.
  • the characteristic signal of each bit can be averaged.
  • the crystal grains of the electrode layer 2 are further microcrystalline than the crystal grains of the ferroelectric recording layer 3. This is due to the fact that when the ferroelectric recording layer 3 is formed, the ferroelectric recording layer 3 grows following the particles of the electrode layer 2, so that the particle diameter tends to increase toward the upper layer.
  • the Pb (Zr x , Ti 1-x ) O 3 [PZT] crystal grains constituting the ferroelectric recording layer 3 are made of electrodes having the same (particle) crystal structure with different components and compositions.
  • microcrystals for example, 30 nm or less
  • the electrode layer 2 and the ferroelectric recording layer 3 can be configured non-oriented.
  • the SRO film is formed without sputtering by forming the SRO film on the amorphous SiO 2 layer by sputtering, and when PZT film is formed on the non-oriented SRO film, the PZT film turns into the SRO film. It becomes non-oriented following.
  • non-orientation means that the rocking curve that can be confirmed by XRD does not substantially peak as shown in FIG. 3 (some peaks can be made from the configuration of the X-ray measuring apparatus and the shape as a film). ) And this non-orientation (or amorphous) makes it possible to average the whole or locally instead of reducing the resolution (polarization amount (value)) of the ferroelectric recording layer 3. As compared with the case of being oriented, averaging can be easily realized.
  • the concentration of Pb (DPM) 2 as the Pb raw material is adjusted in the process of forming the film from the electrode layer 2 side to the upper layer in the range of 0.14 ml / min to 0.16 ml / min. For example, by reducing the concentration in the lower layer and increasing the concentration in the upper layer, the Pb concentration in the uppermost layer at the time of completion of the information recording / reproducing memory medium is set to 20% to 22% (atomic%). The conductivity of the dielectric recording layer 3 may be lowered. It is preferable to shift the Pb concentration from the stoichiometric ratio to the higher one.
  • Pb On the lower layer side of the recording layer, Pb may be a value satisfying the stoichiometric ratio or a value shifted to a smaller value. If the Pb concentration is high in the lower layer, the diffusion of SRO is promoted too much and leaks, and if the Pb content is low in the upper layer, the ferroelectricity may be impaired. Further, it is preferable that the ratio of the Zr raw material to the Ti raw material is 4: 6. Thus, a gradient change may be provided in the film formation stage. Further, post-annealing may be performed after providing a gradient change in the concentration in the film formation stage. In that case, Pb diffuses into the electrode layer, and Sr diffuses into the recording layer. That is, mutual diffusion also occurs.
  • the composition of the electrode layer 2 and the ferroelectric recording layer 3 is inclined, that is, the electrode layer 2 and the ferroelectric recording layer 3 are continuous.
  • the ferroelectric recording layer 3 is mixed with a conductive portion and an insulating portion (for example, mesh shape or spiral shape), so that the surface charge at the time of polarization inversion of the ferroelectric recording layer 3 is excessive or insufficient. It is also possible to suppress the occurrence of (prevent charge-up). Note that when the conductive portion and the insulating portion are mixed in a mesh shape, a conductive material (metal or highly doped semiconductor) may be introduced.
  • the thickness of the ferroelectric recording layer 3 is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 10 to 1000 nm, and more preferably 50 to 500 nm.
  • the ferroelectric recording layer 3 has a surface roughness (RMS) measured by an atomic force microscope (AFM) of, for example, 30 nm or less or a little larger than that when formed by the MOCVD method or the like. Become.
  • the case of the ferroelectric recording layer 3 has been described.
  • a non-oriented structure of microcrystals microcrystallites
  • a magnetic material or It can also be applied to a recording medium such as optical recording.
  • the recording layer grows following the base electrode layer (for example, SRO film). If the base is fine, it grows to fine particles, and if the base is non-oriented, it grows unoriented. In addition, particles grow in the upper layer.
  • FIG. 4 shows the influence of the deposition amount of the ferroelectric recording layer 3 on the particle diameter.
  • the ferroelectric recording layer (PZT) 3 When the ferroelectric recording layer (PZT) 3 is deposited on the upper layer of the electrode layer (SRO) 2 by 400 nm, it becomes a serious state.
  • the ferroelectric recording layer 3 grows as fine particles using the particles of the electrode layer 2 as nuclei, but the particle size of the fine particles increases as it goes to the upper layer. Therefore, in order to increase the particle size of the fine particles, it is preferable to increase the amount of the ferroelectric recording layer 3 deposited.
  • the deposition amount is preferably 100 nm.
  • FIG. 5 shows an example of the relationship between the particle diameter and the recording mark diameter.
  • the shape of each pit (lattice shape) and the variation in signal intensity increase.
  • the diffusion atom has a composition larger than the stoichiometric ratio in the film.
  • the amount of the organometallic complex containing the component in the liquid source is adjusted in the MOCVD deposition method in order to obtain the desired composition ratio (for example, Pb) from the stoichiometric ratio. This can be easily achieved.
  • RTA Post-annealing
  • This heat treatment includes diffusion from the ferroelectric layer 3 to the electrode layer 2 (for example, diffusion of Pb to the electrode layer 2) and diffusion from the electrode layer 2 to the ferroelectric layer 3 (for example, Sr ferroelectric layer). (Diffusion to 3) is preferably caused. That is, it is preferable to cause mutual diffusion between the electrode layer 2 and the ferroelectric layer 3.
  • the heat treatment temperature is determined by diffusion from the ferroelectric layer 3 to the electrode layer 2, diffusion from the electrode layer 2 to the ferroelectric layer 3, or diffusion from the ferroelectric layer 3 to the electrode layer 2 and strong from the electrode layer 2. This is the temperature at which diffusion into the dielectric layer 3 occurs.
  • a temperature higher than the film forming temperature of the recording layer 2 is preferable. 500 to 700 ° C is preferable. More preferably, the temperature is from 550 ° C to 700 ° C.
  • FIG. 6 shows the state of change between the ferroelectric recording layer 3 and the electrode layer 2 when the temperature of the RTA is changed.
  • the film forming conditions in FIG. 6 are as follows.
  • Electrode layer Sputtering Target: SRO Parallel plate electrode Frequency: 13.56 MHz Gas: Ar + O 2 Thickness: 50nm
  • Recording layer: MOCVD Solvent Pb (DPM) 2 : 0.1 ml / min Zr (dmhd) 4 : 0.07 ml / min Ti (O-iPr) 2 (DPM) 2 : 0.13 ml / min Pb x (Zr 0.4 , Ti 0.6 ) O 3 x 1.1 Thickness: 100nm
  • RTA Temperature rising rate: 100 ° C./sec
  • the boundary between the ferroelectric recording layer 3 and the electrode layer 2 becomes unclear. Further, particles composed of a partial component of PZT and a partial component of SRO are formed.
  • FIG. 3 shows the effect of shifting the amount of Pb from the stoichiometric ratio.
  • FIG. 3 is a graph showing the effect of Pb amount and diffusion.
  • the measurement is a measurement value after RTA and before CMP.
  • Measurement is performed by etching from the surface of the film at an etching rate of about 8 nm / min and measuring the concentration of each component element.
  • the heat treatment time is preferably 5 seconds or more and 5 minutes or less. If it is less than 5 seconds, sufficient diffusion may not occur. In 5 minutes or more, the constituent atoms may escape from the film. Further, it is preferable to diffuse from the electrode layer 2 to the opposite surface of the ferroelectric layer 3. Further, it is preferable that the diffusion atoms are diffused so as to generate a concentration gradient. Generally, it diffuses with a concentration gradient. If the diffusion distance and the amount of diffusion are examined in advance at actual temperatures and times by experiments, the diffusion distance and concentration gradient can be easily controlled.
  • the heat treatment with the above temperature and time improves crystallization or crystallinity and provides excellent ferroelectric properties.
  • the heat treatment atmosphere is not particularly limited, but an oxidizing atmosphere is preferable.
  • the heating rate from room temperature to the above heat treatment temperature is preferably 50 ° C./sec or more. When the heating rate is less than 50 ° C./sec, a non-ferroelectric phase crystal (pyrochlore phase) is generated.
  • the protective layer 4, the surface layer 5, and the lubricating layer 6 are formed on the ferroelectric recording layer 3 of the obtained Pb (Zry , Ti 1-y ) O 3 [PZT] using a sputtering method or the like. You may form sequentially.
  • the protective layer 4 has a finer particle or amorphous structure (high dielectric constant) than that of the ferroelectric recording layer 3, and is composed of the same composition ratio as that of the ferroelectric recording layer.
  • the protective layer 4 or the ferroelectric Changes in characteristics (recrystallization) as a whole including the body recording layer 3 can be mitigated.
  • CMP CMP CMP is performed to planarize the surface and achieve a desired thickness.
  • a method used for polishing a normal silicon semiconductor can be used.
  • the surface roughness after CMP is preferably 10 nm or less as Ra.
  • FIG. 7 shows the polarization inversion characteristics before and after CMP. Note that FIG. 7 shows a case where plasma etching processing in a later step is performed.
  • the etching amount is preferably 0 to 5 nm. Further, as the plasma gas, it is preferable to use Ar containing oxygen in order to prevent escape of oxygen.
  • Damage layer is removed by plasma etching.
  • the power in the plasma etching depends on the size of the wafer and the size (capability, etc.) of the apparatus, but in this embodiment, it is preferably 50 W or less.
  • an amorphous layer is formed on the surface of the recording layer 2.
  • This amorphous layer is composed of the same constituent elements as the ferroelectric recording layer 3. If the protective layer 4 is formed on the ferroelectric recording layer 3 with a material containing atoms different from that of the ferroelectric recording layer 3, the different elements are mixed into the ferroelectric recording layer 3 by diffusion or the like. However, there is a possibility that the characteristics of the ferroelectric recording layer 3 may be impaired.
  • the amorphous protective layer 4 is formed by performing plasma etching on the surface of the ferroelectric recording layer 3, it is possible to prevent deterioration of characteristics due to mixing of different elements. Further, by making the protective layer 4 amorphous, it is possible to obtain a memory having excellent grain boundary reading characteristics. That is, at the time of reading with the probe 11, in the case of polycrystal, there is a possibility that electric field concentration occurs at the crystal grain boundary. In this case, local reading variations occur. However, when the protective layer 4 is made amorphous, there is no such variation in reading at the crystal grain boundaries as described above.
  • the protective layer 4 may be amorphized by plasma treatment after polishing its surface by CMP, it can be configured more easily than other amorphized or fine particle layers. .
  • FIG. 8 shows the result of evaluating the effect of plasma etching by the reversal characteristics. As shown in FIG. 8, it can be seen that the inversion characteristics are improved as the etching time is increased.
  • the resolution and the signal intensity (S / N) are deteriorated when the thickness of the protective layer 4 is excessively increased, the microscopic nonuniformity between the signal intensity (S / N) and the resolution is obtained. It is preferable to determine (for example, 0 to 10 nm) in consideration of a trade-off with the relaxation of the thickness.
  • the surface layer 5 may be made of other materials.
  • the film is formed from a material having high strength such as DLC (diamond-like carbon), and it is possible to suppress chemical change and to physically protect the head from a probe or the like.
  • the lubricating layer 6 is made of PFPE or the like, and can reduce friction with a head such as a probe.
  • the lubrication layer 6 can improve the lubrication effect when combined with the hard surface layer 5.
  • a one-bit one capacitor or a ferroelectric gate insulating film is formed.
  • a probe electrode of a memory medium reading device or the like serves as the upper electrode, and a substantially entire surface in the medium surface is continuously formed.
  • the ferroelectric layer 2 can be formed.
  • the ferroelectric layer 2 has some conductivity, the polarization of the ferroelectric layer 2 can be maintained. Accordingly, since both the electrodes are always short-circuited due to the conductivity, it has been difficult to read by the potential (electric field) or the reversal current at the time of polarization reversal. In addition to being able to read out data, it is possible to suppress charge-up on the surface of the medium due to electrical conductivity, although the degree of freedom of the readout method is broadened if it is inherently non-conductive.

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  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention concerne un support pour mémoire d’enregistrement / de reproduction d’informations, capable de réaliser une moyenne locale des propriétés d’une couche d’enregistrement et de garantir de ce fait la stabilisation d’un enregistrement / d’une reproduction. Une couche (2) d’électrode et une couche (3) d’enregistrement sont déposées sur la couche supérieure d’un substrat (1). On fait varier suivant un gradient les compositions des particules granulaires disposées sur la couche (2) d’électrode et la couche (3) d’enregistrement. En l’occurrence, il est possible de constituer une particule en colonne continue de la couche (2) d’électrode à la couche (3) d’enregistrement et de former une partie présentant une certaine conductivité (une partie conductrice). Il est donc possible de limiter l’accumulation de charges et de maintenir un aspect cristallin prononcé.
PCT/JP2008/064221 2008-08-07 2008-08-07 Support pour mémoire d’enregistrement / de reproduction d’informations et procédé pour sa fabrication WO2010016130A1 (fr)

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CN104538539A (zh) * 2014-12-25 2015-04-22 内蒙古科技大学 一种电卡效应致冷复合厚膜材料

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JPH09198729A (ja) * 1995-11-17 1997-07-31 Tdk Corp 記録媒体およびその製造方法ならびに情報処理装置
JP2003281793A (ja) * 2002-03-26 2003-10-03 Pioneer Electronic Corp 誘電体記録媒体とその製造方法及びその製造装置

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JPH11316983A (ja) * 1998-05-06 1999-11-16 Nikon Corp 情報記録媒体、情報書き込み方法及び情報読み出し方法
US6822277B2 (en) * 2000-08-24 2004-11-23 Rohm Co. Ltd. Semiconductor device and method for manufacturing the same
JP4040397B2 (ja) * 2002-08-29 2008-01-30 富士通株式会社 容量素子を有する装置とその製造方法
KR100813517B1 (ko) * 2006-10-27 2008-03-17 삼성전자주식회사 데이터 저장을 위한 강유전체 박막의 제조방법 및 이를이용한 강유전체 기록매체의 제조방법

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JPH09198729A (ja) * 1995-11-17 1997-07-31 Tdk Corp 記録媒体およびその製造方法ならびに情報処理装置
JP2003281793A (ja) * 2002-03-26 2003-10-03 Pioneer Electronic Corp 誘電体記録媒体とその製造方法及びその製造装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104538539A (zh) * 2014-12-25 2015-04-22 内蒙古科技大学 一种电卡效应致冷复合厚膜材料

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