WO2016111280A1 - 圧電薄膜及び圧電振動子 - Google Patents
圧電薄膜及び圧電振動子 Download PDFInfo
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- WO2016111280A1 WO2016111280A1 PCT/JP2016/050092 JP2016050092W WO2016111280A1 WO 2016111280 A1 WO2016111280 A1 WO 2016111280A1 JP 2016050092 W JP2016050092 W JP 2016050092W WO 2016111280 A1 WO2016111280 A1 WO 2016111280A1
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- thin film
- piezoelectric thin
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- 239000010409 thin film Substances 0.000 title claims abstract description 71
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 229910021478 group 5 element Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 229910001849 group 12 element Inorganic materials 0.000 claims description 5
- 229910021480 group 4 element Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 37
- 239000000758 substrate Substances 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 239000011777 magnesium Substances 0.000 description 19
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 239000010955 niobium Substances 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910052706 scandium Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000000095 laser ablation inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 230000001151 other effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000012621 laser-ablation inductively coupled plasma technique Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052696 pnictogen Inorganic materials 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
- H03H9/15—Constructional features of resonators consisting of piezoelectric or electrostrictive material
- H03H9/17—Constructional features of resonators consisting of piezoelectric or electrostrictive material having a single resonator
- H03H9/171—Constructional features of resonators consisting of piezoelectric or electrostrictive material having a single resonator implemented with thin-film techniques, i.e. of the film bulk acoustic resonator [FBAR] type
- H03H9/172—Means for mounting on a substrate, i.e. means constituting the material interface confining the waves to a volume
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0617—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
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- H03H3/007—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks
- H03H3/02—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of piezoelectric or electrostrictive resonators or networks
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- H03H9/05—Holders; Supports
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- H03H9/2468—Tuning fork resonators
- H03H9/2478—Single-Ended Tuning Fork resonators
- H03H9/2489—Single-Ended Tuning Fork resonators with more than two fork tines
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- H03H2003/027—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of piezoelectric or electrostrictive resonators or networks the resonators or networks being of the microelectro-mechanical [MEMS] type
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- H03H3/02—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of piezoelectric or electrostrictive resonators or networks
- H03H3/04—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of piezoelectric or electrostrictive resonators or networks for obtaining desired frequency or temperature coefficient
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- H03H3/04—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of piezoelectric or electrostrictive resonators or networks for obtaining desired frequency or temperature coefficient
- H03H2003/0414—Resonance frequency
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- H03H9/02015—Characteristics of piezoelectric layers, e.g. cutting angles
- H03H9/02031—Characteristics of piezoelectric layers, e.g. cutting angles consisting of ceramic
Definitions
- the present invention relates to a piezoelectric thin film and a piezoelectric vibrator.
- Patent Document 1 discloses that a piezoelectric thin film of a piezoelectric vibrator uses a ScAlN (scandium-containing aluminum nitride) film in which Sc (scandium) is added to AlN (aluminum nitride) to improve the piezoelectric characteristics of the piezoelectric vibrator. It is disclosed.
- the present invention has been made in view of such circumstances, and an object thereof is to provide a piezoelectric thin film and a piezoelectric vibrator capable of reducing stress while sufficiently securing piezoelectric characteristics.
- a piezoelectric thin film according to one aspect of the present invention includes an AlN crystal, at least one first element that is replaced with Al in the AlN crystal, and ions that are smaller than the ion radius of the first element and larger than the ion radius of Al.
- FIG. 3 is a schematic diagram of a cross section of the piezoelectric vibrator taken along line 3-3 in FIG. 2. It is a table
- FIG. 3 is a schematic diagram of a cross section of the piezoelectric vibrator taken along line 3-3 in FIG. 2. It is a table
- FIG. 8 is a schematic view of a cross section of a piezoelectric vibrator taken along line 8-8 in FIG.
- FIG. 9 is a table corresponding to FIG. 6 and showing the result of verifying the effect in the second embodiment of the present invention. It is a table
- FIG. 1 is a perspective view schematically showing an appearance of a piezoelectric vibration device 10 according to one specific example.
- the piezoelectric vibration device 10 includes a lower substrate 11, an upper substrate 12 that forms a vibration space between the lower substrate 11, a piezoelectric vibrator 13 that is sandwiched between the lower substrate 11 and the upper substrate 12, and It has.
- the piezoelectric vibrator 13 is a MEMS vibrator manufactured using the MEMS technology.
- the piezoelectric vibration device 10 functions as a timing device incorporated in an electronic device such as a smartphone.
- FIG. 2 is an exploded perspective view schematically showing the structure of the piezoelectric vibration device 10 according to one specific example.
- the piezoelectric vibrator 13 includes a support frame 14 that spreads in a rectangular frame shape along the XY plane in the orthogonal coordinate system of FIG. 2, and an XY plane in the support frame 14 from one end of the support frame 14.
- a plurality of resonating arms 16 extending along the XY plane from a fixed end connected to one end of the base 15 toward the free end.
- four vibrating arms 16 extend in parallel to the Y axis. Note that the number of vibrating arms 16 is not limited to four, and is set to an arbitrary number of three or more, for example.
- FIG. 3 is a schematic diagram of a cross section of the piezoelectric vibrator 13 taken along line 3-3 in FIG.
- the lower substrate 11 extends in a flat plate shape along the XY plane, and a concave portion 17 is formed on the upper surface thereof.
- the concave portion 17 is formed in a flat rectangular parallelepiped shape, for example, and forms a part of the vibration space of the vibrating arm 16.
- the upper substrate 12 extends in a flat plate shape along the XY plane, and a recess 18 is formed on the lower surface thereof.
- the recess 18 is formed in a flat rectangular parallelepiped shape, for example, and forms a part of the vibration space of the vibrating arm 16.
- the support frame 14 of the piezoelectric vibrator 13 is received on the peripheral edge of the upper surface of the lower substrate 11 defined outside the recess 17, and the recess is formed on the support frame 14 of the piezoelectric vibrator 13.
- the peripheral edge of the lower surface of the upper substrate 12 defined outside 18 is received.
- the piezoelectric vibrator 13 is held between the lower substrate 11 and the upper substrate 12, and the vibration space of the vibrating arm 16 is formed by the lower substrate 11, the upper substrate 12, and the support frame 14 of the piezoelectric vibrator 13. .
- This vibration space is kept airtight and a vacuum state is maintained.
- Both the lower substrate 11 and the upper substrate 12 are made of Si (silicon).
- the vibrating arm 16 sandwiches the SiO 2 layer 21, the Si layer 22 stacked on the SiO 2 layer 21, the piezoelectric thin film 23 stacked on the Si layer 22, and the piezoelectric thin film 23.
- the SiO 2 layer 21 may be formed on the upper surface or the lower surface of the piezoelectric thin film 23.
- a silicon oxide material including an appropriate composition of the Si a O b layer (a and b are integers) is used.
- the Si layer 22 is formed of an n-type Si semiconductor that is a degenerate semiconductor, and includes a Group 15 element such as P (phosphorus), As (arsenic), and Sb (antimony) as an n-type dopant.
- P (phosphorus) is used as the n-type dopant of the Si layer 22.
- the lower electrode 24 and the upper electrode 25 for example, Mo (molybdenum), Ru (ruthenium), Pt (platinum), Ti (titanium), Cr (chromium), Al (aluminum), Cu (copper), Ag ( Silver) or a metal material such as an alloy thereof is used.
- the lower electrode 24 and the upper electrode 25 are each connected to an AC power source (not shown) provided outside the piezoelectric vibration device 10.
- an electrode (not shown) formed on the upper surface of the upper substrate 12 or a through silicon via (TSV) (not shown) formed in the upper substrate 12 is used.
- the piezoelectric thin film 23 includes an AlN (aluminum nitride) crystal as a main component, at least one first element replaced with Al in the AlN crystal, and an ion of Al (aluminum) that is smaller than the ion radius of the first element. And a second element added to the AlN crystal and having an ionic radius larger than the radius.
- AlN aluminum nitride
- a second element added to the AlN crystal and having an ionic radius larger than the radius.
- the Group 3 element may be contained in the first element, both the Group 2 element and the Group 4 element may be contained, or both the Group 2 element and the Group 5 element are contained.
- Sc scandium
- Y yttrium
- Mg magnesium
- Ca calcium
- Sr sinrontium
- Ti titanium
- Zr zirconium
- Hf hafnium
- V vanadium
- Nb niobium
- Zn (zinc) is selected as the Group 12 element.
- FIG. 4 shows the valence, coordination number and ionic radius of the main components AlN (Al, N) and the first element (Sc, Y, Mg, Ca, Sr, Zr, Hf, V, Nb, Zn). It is a table
- the piezoelectric thin film 23 has a wurtzite structure and is oriented substantially perpendicular to the Si layer 22 on the c-axis.
- a voltage is applied in the c-axis direction by the lower electrode 24 and the upper electrode 25, the piezoelectric thin film 23 expands and contracts in a direction substantially perpendicular to the c-axis.
- the vibrating arm 16 is bent and displaced in the Z-axis direction, and its free ends are displaced toward the inner surfaces of the lower substrate 11 and the upper substrate 12, and vibrates in an out-of-plane bending vibration mode.
- the second element has an ion radius smaller than that of the first element and larger than that of Al (aluminum). Further, as will be described later, the second element is preferably present as a trivalent cation.
- the second element is selected from, for example, W (tungsten), Zr (zirconium), Fe (iron), Ta (tantalum), Cr (chromium), Ti (titanium), and Ni (nickel). At least one element selected is used.
- FIG. 5 is a table showing the valence, coordination number, and ionic radius of each second element. Zr is shown in FIG.
- Sc of the Group 3 element is selected as the first element.
- the ratio of the number of Sc atoms to the total amount of Al atoms and Sc atoms in the piezoelectric thin film 23 (hereinafter also referred to as “Sc composition ratio”) is 0.03 or more and 0.50. It is preferable to set as follows.
- the ratio of the number of atoms of the second element to the total number of Al atoms and Sc atoms in the piezoelectric thin film 23 (hereinafter also referred to as “content”) is 0.01 at% or more and 1.00 at% or less. It is preferably set. Details of these numerical ranges are described below.
- a piezoelectric thin film was formed for each of the comparative example and the example, and stress and piezoelectric characteristics of the formed piezoelectric thin film were measured.
- RF magnetron sputtering was performed on a 3-inch diameter Si substrate based on an alloy target having a predetermined composition having a 3-inch diameter.
- a piezoelectric thin film having a predetermined composition was formed on the Si substrate with a thickness of 1.0 ⁇ m.
- Sc is used as the first element
- W, Zr, Ta, Ti, Cr, Ni, and Fe are used as the second element.
- the composition of the target was adjusted according to the composition of the piezoelectric thin film.
- the RF power was set to 300 W
- the flow rate of Ar (argon) gas was set to 30 sccm
- the flow rate of N2 (nitrogen) gas was set to 15 sccm in the chamber.
- the temperature of the Si substrate was set to 200 ° C.
- the back pressure was set to 1.0 ⁇ 10 ⁇ 4 Pa
- the film forming pressure was set to 1.0 ⁇ 10 ⁇ 1 Pa.
- the stress [MPa] in the piezoelectric thin film formed under the above conditions and the piezoelectric characteristics (piezoelectric constant d33) [pC / N] of the piezoelectric thin film were measured.
- the piezoelectric constant was measured based on the Berlincourt method using a measuring device PM100 manufactured by Piezotest.
- the composition of the piezoelectric thin film was analyzed based on the LA-ICP-MS method (laser ablation ICP mass spectrometry: Laser Ablation Inductively Coupled Plasma Mass Spectrometry).
- the valence and coordination number of the elements contained in the piezoelectric thin film were analyzed based on X-ray absorption spectroscopy (XAFS).
- FIG. 6 is a table showing the results of verifying the effects of the present invention.
- the Sc composition ratio means the ratio of the number of Sc atoms to the total number of Al atoms and the first element in the piezoelectric thin film 23 as described above.
- the content means the ratio of the number of atoms of the second element to the total number of Al atoms and Sc atoms in the piezoelectric thin film 23, and is expressed in atomic composition percentage (at%).
- ScAlN films were formed as piezoelectric thin films of Comparative Examples 1 to 8. In the piezoelectric thin films of Comparative Examples 1 to 8, the Sc composition ratio was changed. The second element was not added to the piezoelectric thin film.
- the Sc composition ratio is increased in the same manner as in Comparative Examples 1 to 7, while the ionic radius is smaller than the ionic radius of Sc and larger than the ionic radius of Al.
- W was added as a second element having: The W content was set to 0.50 at%. The definition of the content is as described above. For example, in Example 1, it means that the Sc composition ratio is 0.03 and the W content is 0.50 at%.
- the stress was reduced while the piezoelectric constant was increased as compared with Comparative Examples 1 to 7. According to the results of Examples 1 to 7, the stress reduction and the piezoelectric constant increase can be realized simultaneously by the inclusion of the second element W.
- Comparative Example 9 a piezoelectric thin film in which W was added as a second element to Comparative Example 8 was formed.
- the piezoelectric thin film of Comparative Example 9 was able to reduce stress compared with the piezoelectric thin film of Comparative Example 8, but it was found that the piezoelectric constant was zero.
- the Sc composition ratio is preferably set to 0.03 (Example 1) or more and 0.50 (Example 7) or less.
- Examples 8 to 13 piezoelectric thin films each containing Zr, Ta, Ti, Cr, Ni, and Fe as the second element were formed.
- the Sc composition ratio was set to 0.40, and the content of the second element was set to 0.50 at%.
- the stress is reduced and the piezoelectric constant is increased.
- Examples 14 to 21 piezoelectric thin films containing Fe as the second element were formed.
- the Sc composition ratio was set to 0.40, and the content of the number of atoms of the second element was 0.005 (Example 14) at% or more and 1.10 (Example 21) at%. Set as follows.
- all of Examples 14 to 21 were able to simultaneously realize a reduction in stress and an increase in piezoelectric constant. Furthermore, it was confirmed that the piezoelectric constant can be maintained high while the stress decreases as the content of the second element increases.
- Example 21 in which the content of the second element was set to 1.10 at% was compared with Example 20 in which the content of the second element was set to 1.00 at%.
- the piezoelectric constant is relatively reduced.
- the content of the second element is set to 0.005 at%.
- the decrease in stress is slight compared to Comparative Example 6 in which the Sc composition ratio is 0.40.
- the content of the second element in the piezoelectric thin film is preferably 0.005 at% or more and 1.10 at% or less, particularly preferably 0.01 at% or more and 1.00 at% or less. It was confirmed.
- the second element when the second element is present as a trivalent cation as in Examples 9 to 21, it is confirmed that the stress tends to decrease particularly and the piezoelectric constant tends to increase particularly. It was. According to this result, it was found that the second element is particularly effective when it exists as a trivalent cation. Further, it has been found that the effect is particularly effective when the coordination number of the second element is 4 or 6 as in Examples 1 to 21. From the above, it was confirmed that the second element was particularly effective when the composition ratio of the first element, the content of the second element, the valence, and the coordination number were set within the above numerical ranges.
- FIG. 7 is an exploded perspective view schematically showing a structure showing an appearance of a piezoelectric vibration device 30 according to another specific example.
- the piezoelectric vibration device 30 includes a piezoelectric vibrator 33 that vibrates in an in-plane vibration mode instead of the piezoelectric vibrator 13 that vibrates in the bending vibration mode.
- the piezoelectric vibrator 33 is sandwiched between the lower substrate 11 and the upper substrate 12 in the same manner as the piezoelectric vibrator 13 described above.
- the overlapping description is abbreviate
- the piezoelectric vibrator 33 is disposed inside the support frame 34 along the XY plane along the XY plane in the orthogonal coordinate system of FIG.
- the vibration part 35 which spreads in a rectangle, and a pair of connection parts 36 and 36 which connect the support frame 34 and the vibration part 35 to each other are provided.
- the vibration unit 35 vibrates by repeatedly expanding and contracting in the Y-axis direction along the XY plane.
- the support frame 34 includes a pair of long-side frames 34a and 34a extending in parallel to the X axis, and a pair of short frames extending in parallel to the Y axis and connected to both ends of the frames 34a and 34a at both ends thereof.
- the connecting portions 36 and 36 extend on a straight line parallel to the X axis and connect the frame bodies 34b and 34b and the vibrating portion 35 to each other.
- the positions of the connecting portions 36 and 36 are set to an intermediate position in the Y-axis direction of the vibration portion 35, that is, an end portion (node point) of the center position of the vibration portion 35 in the vibration direction.
- FIG. 8 is a schematic diagram of a cross section taken along line 8-8 in FIG.
- the support frame 34, the vibration part 35, and the connection part 36 are composed of the SiO 2 (silicon dioxide) layer 41 and the Si layer 42 stacked on the SiO 2 layer 41.
- the piezoelectric thin film 43 laminated on the Si layer 42, and the lower electrode 44 and the upper electrode 45 formed on the upper and lower surfaces of the piezoelectric thin film 43 and sandwiching the piezoelectric thin film 43 are formed.
- the piezoelectric thin film 43, the lower electrode 44, and the upper electrode 45 are configured in the same manner as the piezoelectric thin film 23, the lower electrode 24, and the upper electrode 25 described above.
- the piezoelectric thin film 43 is C-axis oriented substantially perpendicular to the Si layer 42.
- the vibration unit 35 is excited.
- the vibration part 35 vibrates and contracts in the short side direction, that is, the Y-axis direction.
- stretching vibration that repeats the state in which the vibration part 35 is extended and the state in which the vibration part 35 is contracted occurs.
- the piezoelectric thin film 43 is configured in the same manner as the piezoelectric thin film 23 described above, so that the same function and effect can be realized.
- Group 1 element Mg (valence 2, coordination number 4, ion radius 0.5 nm) and Group 5 element Nb (valence 4, coordination number 8, ion radius as the first element) 0.79 nm) is selected, and Fe (valence 3, coordination number 4, ionic radius 0.49 nm) is selected as the second element.
- the ratio of the number of Mg atoms to the total number of Al atoms, Mg atoms and Nb atoms in the piezoelectric thin film 23 (hereinafter also referred to as “Mg composition ratio”) and The ratio of the number of Nb atoms (hereinafter also referred to as “Nb composition ratio”) is set to 0.2.
- the ratio of the number of atoms of the second element Fe to the total number of Al atoms, Mg atoms and Nb atoms (hereinafter also referred to as “content”) is 0.005 at% or more. It is preferably set to 10 at% or less, and more preferably 0.005 at% or more and 1.00 at% or less. Details of these numerical ranges are described below.
- the effect verification method is the same as in the first embodiment.
- FIG. 9 is a table showing the results of verifying the effects according to the present embodiment.
- the Mg composition ratio and the Nb composition ratio were both 0.2, and the second element was not added.
- the Mg composition ratio and the Nb composition ratio are both set to 0.2, and the content of the second element Fe is 0.005 (Experimental Example 2). -1) At% or more and 1.10 (Experimental Example 2-8) At% or less.
- the Fe content is preferably 0.005 at% or more and 1.10 at% or less, and 0.005 at% or more. It was confirmed that 1.00 at% or less is more suitable.
- the Group 2 element Mg (valence 2, coordination number 4, ionic radius 0.5 nm) and the Group 5 element Hf (valence 4, coordination number 8, ionic radius). 0.83 nm) and Fe (valence 3, coordination number 4, ionic radius 0.49 nm) is selected as the second element.
- the ratio of the number of Mg atoms to the total number of Al atoms, Mg atoms and Hf atoms in the piezoelectric thin film 23 (hereinafter also referred to as “Mg composition ratio”) and The ratio occupied by the number of Hf atoms (hereinafter also referred to as “Hf composition ratio”) is set to 0.25.
- the ratio of the number of atoms of the second element Fe to the total number of Al atoms, Mg atoms, and Hf atoms (hereinafter also referred to as “content”) is 0.005 at% or more. It is preferably set to 10 at% or less, and more preferably 0.005 at% or more and 1.00 at% or less. Details of these numerical ranges are described below.
- the effect verification method is the same as in the first embodiment.
- FIG. 10 is a table showing the results of verifying the effects according to the present embodiment.
- the Mg composition ratio and the Hf composition ratio were both 0.25, and the second element was not added.
- the Mg composition ratio and the Hf composition ratio are both set to 0.25, and the content of the second element Fe is 0.005 (Experimental Example 3). -1) At% or more and 1.10 (Experimental Example 3-8) At% or less.
- the Fe content is preferably 0.005 at% or more and 1.10 at% or less, and 0.005 at% or more. It was confirmed that 1.00 at% or less is more suitable.
- each above embodiment is for making an understanding of this invention easy, and is not for limiting and interpreting this invention.
- the present invention can be changed / improved without departing from the gist thereof, and includes equivalents thereof. That is, those in which the person skilled in the art appropriately changes the design of each embodiment is also included in the scope of the present invention as long as the features of the present invention are included.
- each element included in each embodiment and its arrangement, material, condition, shape, size, and the like are not limited to those illustrated, and may be changed as appropriate.
- each element included in each embodiment is combined as far as technically possible, and a combination thereof is included in the scope of the present invention as long as it includes the features of the present invention.
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Abstract
Description
本実施形態では、第1元素として第2族元素のMg(価数 2、配位数 4、イオン半径 0.5nm)及び第5族元素のNb(価数 4、配位数 8、イオン半径 0.79nm)の両方を選択し、第2元素としてFe(価数 3、配位数4、イオン半径 0.49nm)を選択している。
なお、効果の検証方法については第1の実施形態と同様である。
本実施形態では、第1元素として第2族元素のMg(価数 2、配位数 4、イオン半径 0.5nm)及び第5族元素のHf(価数 4、配位数 8、イオン半径 0.83nm)の両方を選択し、第2元素としてFe(価数 3、配位数4、イオン半径 0.49nm)を選択している。
なお、効果の検証方法については第1の実施形態と同様である。
23 圧電薄膜
24 電極(下側電極)
25 電極(上側電極)
33 圧電振動子
43 圧電薄膜
44 電極(下側電極)
45 電極(上側電極)
Claims (7)
- AlN結晶と、
前記AlN結晶においてAlと置き換えられる少なくとも1つの第1元素と、
前記第1元素のイオン半径よりも小さく、かつ、Alのイオン半径よりも大きなイオン半径を有し、前記AlN結晶に添加される第2元素と、を含有する圧電薄膜。 - 前記第1元素が、第3族元素、又は、第2族元素及び第4族元素、又は、第2族元素及び第5族元素、又は、第12族元素及び第4族元素、又は、第12族元素及び第5族元素である、請求項1に記載の圧電薄膜。
- 前記第1元素がScであり、前記圧電薄膜における前記Alの原子数と前記Scの原子数との総量に対して、前記Scの原子数が占める割合は0.03以上0.50以下である、請求項2に記載の圧電薄膜。
- 前記第2元素が、3価陽イオンとして存在している、請求項1~3のいずれか1項に記載の圧電薄膜。
- 前記第2元素が、W、Zr、Fe、Ta、Cr、Ti及びNiのうちから選択された少なくとも1つの元素である、請求項1~4のいずれか1項に記載の圧電薄膜。
- 前記圧電薄膜における前記Alの原子数と前記第1元素の原子数との総量に対する、前記第2元素の原子数の比率は0.01at%以上1.00at%以下である、請求項1~5のいずれか1項に記載の圧電薄膜。
- 圧電薄膜と、
前記圧電薄膜を挟み込む1対の電極と、を備え、
前記圧電薄膜は、
AlN結晶と、
前記AlN結晶においてAlと置き換えられる少なくとも1つの第1元素と、
前記第1元素のイオン半径よりも小さく、かつ、Alのイオン半径よりも大きなイオン半径を有し、前記AlN結晶に添加される第2元素と、を含有する、圧電振動子。
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SG11201705362YA SG11201705362YA (en) | 2015-01-06 | 2016-01-05 | Piezoelectric thin film and piezoelectric transducer |
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JPWO2016111280A1 (ja) | 2017-08-17 |
JP6468468B2 (ja) | 2019-02-13 |
CN107112977B (zh) | 2020-07-14 |
SG11201705362YA (en) | 2017-08-30 |
US20170294894A1 (en) | 2017-10-12 |
CN107112977A (zh) | 2017-08-29 |
US10965270B2 (en) | 2021-03-30 |
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