WO2012160972A1 - 圧電素子用下部電極およびそれを備えた圧電素子 - Google Patents
圧電素子用下部電極およびそれを備えた圧電素子 Download PDFInfo
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- WO2012160972A1 WO2012160972A1 PCT/JP2012/061855 JP2012061855W WO2012160972A1 WO 2012160972 A1 WO2012160972 A1 WO 2012160972A1 JP 2012061855 W JP2012061855 W JP 2012061855W WO 2012160972 A1 WO2012160972 A1 WO 2012160972A1
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- thin film
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- 239000010409 thin film Substances 0.000 claims abstract description 90
- 239000000758 substrate Substances 0.000 claims description 49
- 239000002245 particle Substances 0.000 claims description 23
- 238000002441 X-ray diffraction Methods 0.000 claims description 17
- 229910003087 TiOx Inorganic materials 0.000 claims description 14
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 14
- 230000003746 surface roughness Effects 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 117
- 239000010408 film Substances 0.000 description 54
- 239000013078 crystal Substances 0.000 description 40
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 30
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 30
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 2
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N2/00—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction
- H02N2/0005—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction producing non-specific motion; Details common to machines covered by H02N2/02 - H02N2/16
- H02N2/0075—Electrical details, e.g. drive or control circuits or methods
- H02N2/0085—Leads; Wiring arrangements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/06—Forming electrodes or interconnections, e.g. leads or terminals
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
- H10N30/079—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing using intermediate layers, e.g. for growth control
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/704—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings
- H10N30/706—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings characterised by the underlying bases, e.g. substrates
- H10N30/708—Intermediate layers, e.g. barrier, adhesion or growth control buffer layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/87—Electrodes or interconnections, e.g. leads or terminals
- H10N30/877—Conductive materials
Definitions
- the present invention relates to a piezoelectric element lower electrode serving as a lower electrode of a piezoelectric thin film formed on a substrate, and a piezoelectric element including the lower electrode.
- piezoelectric materials such as Pb (Zr, Ti) O 3 have been used as electromechanical transducers for application to drive elements and sensors.
- Such a piezoelectric body is expected to be applied to a MEMS (Micro Electro Mechanical Systems) element by being formed as a thin film on a substrate such as Si.
- MEMS Micro Electro Mechanical Systems
- the cost can be greatly reduced by manufacturing the elements at a high density on a relatively large Si wafer having a diameter of 6 inches or 8 inches, compared to single wafer manufacturing in which the elements are individually manufactured. it can.
- the piezoelectric thin film and making the device MEMS the mechanical and electrical conversion efficiency is improved, and new added value such as improved sensitivity and characteristics of the device is also created.
- a thermal sensor it is possible to increase measurement sensitivity by reducing thermal conductance due to MEMS, and in an inkjet head for a printer, high-definition patterning can be achieved by increasing the density of nozzles.
- a piezoelectric thin film (hereinafter also referred to as a piezoelectric thin film) formed on a Si substrate is a polycrystal (columnar crystal) in which a plurality of crystals are gathered in a columnar shape because the lattice constant of the crystal is different from that of Si. It becomes.
- a polycrystal columnar crystal
- the more the crystals grown on the same crystal plane in the film thickness direction the higher the orientation
- the larger the columnar crystals the higher the piezoelectric characteristics of the film.
- a device to which a piezoelectric thin film is applied adopts a configuration in which a lower electrode, a piezoelectric thin film, and an upper electrode are sequentially laminated on a substrate such as Si.
- each layer is formed using the lower layer as a base, and thus grows with a considerable influence from the lower layer. That is, when attention is paid to the piezoelectric thin film, the crystallinity of the piezoelectric thin film becomes better as the crystallinity of the lower electrode in the lower layer becomes better.
- the larger the particle size of the constituent metal of the lower electrode the larger the columnar crystals of the piezoelectric thin film, and the higher the orientation of the piezoelectric thin film.
- the surface roughness of the lower electrode is an important factor affecting the orientation of the piezoelectric thin film because it affects the crystal growth in the initial stage of the piezoelectric thin film formation.
- a seed layer including at least one constituent element of a piezoelectric thin film and a lower electrode are sequentially laminated on a substrate, and an arithmetic average roughness Ra of the surface of the lower electrode is 0.5.
- Patent Document 2 when an electrode film is formed on a substrate, first, initial crystal nuclei of the electrode material are formed in an island shape on the substrate (step A), and then the initial crystal nuclei are grown. Thus, a growth layer of the electrode material is formed (step B). At this time, the substrate temperature in the process A is set higher than the substrate temperature in the process B, thereby forming an electrode film with good crystallinity.
- Patent Document 2 discloses that the half-value width of the rocking curve is 1.80 ° for the electrode film, which confirms that an electrode film with good crystallinity is formed.
- Patent Document 3 in a dielectric thin film capacitor in which a dielectric thin film having a perovskite crystal structure is sandwiched between upper and lower electrodes, the average crystal grain size of a Pt layer as a lower electrode is 50 nm or less, and in X-ray diffraction By setting the half-value width of the rocking curve of the (111) plane of Pt to 5 ° or less, the crystallinity and roughness of the dielectric thin film above the Pt layer are improved, and the characteristics (eg, dielectric constant) of the dielectric thin film are improved. It is improving.
- Patent Document 4 in a piezoelectric element in which a Pt layer as a lower electrode is formed on a substrate and a PZT thin film is formed thereon, the half width of the rocking curve in the Pt layer is set to 5 ° or less. The crystal orientation of the PZT thin film above the Pt layer is improved to obtain a large amount of piezoelectric displacement.
- JP 2007-281238 A see claim 5, paragraphs [0037], [0057], [0062], etc.
- JP 2004-311922 A (refer to claim 1, paragraph [0053], FIG. 4 etc.)
- JP 2000-68454 A (refer to claims 1 and 2, paragraphs [0011], [0012], [0014], FIG. 1, FIG. 2, etc.)
- JP 2003-17767 A (refer to claim 1, paragraphs [0009], [0040], etc.)
- the crystallinity and orientation of Pt constituting the lower electrode depend on Pt film formation conditions (for example, substrate temperature during film formation). For this reason, in order to stably form a Pt layer having good characteristics, the average roughness of the surface of the Pt layer as well as the half-value width of the rocking curve is anticipated in anticipation of changes in the Pt film formation conditions. And the average particle size must be controlled simultaneously.
- Patent Documents 1 to 4 the half-value width of the rocking curve, the average roughness of the surface, and the average particle diameter are not all specified simultaneously for the Pt layer, and therefore, a Pt layer with good characteristics is stable. Film formation cannot be performed. As a result, a piezoelectric thin film with good characteristics cannot be stably formed on the Pt layer.
- Patent Documents 1 to 4 do not disclose any point about increasing the average particle diameter of Pt constituting the lower electrode in order to improve the orientation of the piezoelectric thin film.
- Patent Document 3 since the average particle size of Pt is 50 nm at most and cannot be said to be sufficiently large, it is considered that the orientation of the piezoelectric thin film cannot be sufficiently improved.
- a piezoelectric element having a piezoelectric thin film may include a diffusion prevention layer for preventing diffusion of atoms (for example, Pb) in PZT to the substrate side, and an orientation control layer, but there is a gap between the piezoelectric thin film and the substrate. Since the lower electrode always exists, the influence of the crystallinity, surface roughness, and grain size of the lower electrode on the piezoelectric thin film is inevitable. Therefore, in order to stably form a piezoelectric thin film having good characteristics, it is important to appropriately control the characteristics of the lower electrode.
- atoms for example, Pb
- the present invention has been made in order to solve the above-described problems.
- the object of the present invention is to obtain the rocking curve half-value width, the average surface roughness, and the average particle diameter of the Pt layer as the lower electrode all at the same time.
- a lower electrode for a piezoelectric element capable of stably forming a Pt layer with good characteristics and stably forming a piezoelectric thin film with good characteristics on the Pt layer;
- Another object is to provide a piezoelectric element having the lower electrode.
- a lower electrode for a piezoelectric element that serves as a lower electrode of a piezoelectric thin film formed on a substrate, and the lower electrode is composed of a Pt layer, and in the Pt layer, Pt in X-ray diffraction is obtained.
- the (111) plane rocking curve has a half-value width of 2.2 ° or less, a root mean square roughness RMS of 1.0 nm or less, and a Pt average particle size of 200 nm or more.
- a lower electrode for a device is provided.
- a lower electrode for a piezoelectric element that serves as a lower electrode of a piezoelectric thin film formed on a substrate.
- the lower electrode is composed of a Pt layer.
- the half-value width of the rocking curve of the (111) plane of Pt in diffraction is 2.2 ° or less, the arithmetic average roughness Ra of the surface is 0.8 nm or less, and the average particle size of Pt is 200 nm or more.
- a lower electrode for a piezoelectric element is provided.
- a piezoelectric thin film having good characteristics can be stably formed on the lower electrode.
- FIGS. 4A to 4E are cross-sectional views illustrating the manufacturing steps of the piezoelectric element of Example 1.
- FIGS. It is a graph which shows the relationship between the substrate temperature when forming Pt as a lower electrode of the piezoelectric element, and the half width of the rocking curve of the (111) plane of Pt in X-ray diffraction.
- FIG. 10 is a graph showing the result of evaluation by XRD 2 ⁇ / ⁇ measurement for a piezoelectric thin film (PZT film) formed on the lower electrode of Comparative Example 3.
- 6 is a graph showing the result of evaluation by XRD 2 ⁇ / ⁇ measurement for a piezoelectric thin film (PZT film) formed on a lower electrode of Comparative Example 2.
- FIG. 1 is a cross-sectional view showing a schematic configuration of the piezoelectric element 1 of the present embodiment.
- the piezoelectric element 1 is configured by forming a thermal oxide film 12, an adhesion layer 13, a lower electrode 14, a piezoelectric thin film 15, and an upper electrode 16 in this order on a substrate 11.
- the substrate 11 is composed of, for example, a semiconductor substrate made of single crystal Si (silicon) or an SOI (Silicon on Insulator) substrate.
- the thermal oxide film 12 is made of, for example, SiO 2 (silicon dioxide) and is provided for the purpose of protecting and insulating the substrate 11.
- the adhesion layer 13 is composed of a layer of TiOx (titanium oxide) such as TiO 2 (titanium dioxide), and the thermal oxide film 12 and the lower electrode 14 are adhered to each other to prevent peeling at the interface between them. It is provided for the purpose.
- the lower electrode 14 is an electrode (lower electrode for piezoelectric element) located in the lower layer of the piezoelectric thin film 15, and is composed of Pt (platinum).
- the upper electrode 16 is an electrode located in the upper layer of the piezoelectric thin film 15, and is made of, for example, Pt.
- the upper electrode 16 may be formed of, for example, a Ti (titanium) layer and a Pt layer, and the Ti layer may be used as an adhesion layer between the Pt layer and the piezoelectric thin film 15.
- the piezoelectric thin film 15 is composed of a thin film of PZT (lead zirconate titanate) which is a kind of piezoelectric material.
- FIG. 2 schematically shows the crystal structure of PZT.
- the crystal structure shown in the figure is called a perovskite structure.
- the perovskite structure is a Pb (Zr x , Ti 1-x ) O 3 tetragonal crystal in which a Pb (lead) atom is located at each vertex of the tetragonal crystal, and a Ti atom or Zr (zinc) atom is located in the body center. It is a structure in which O (oxygen) atoms are located at each face center.
- a piezoelectric body is known to exhibit a good piezoelectric effect when the crystal structure has a perovskite structure. Therefore, in the piezoelectric element 1 of the present embodiment, a good piezoelectric effect can be obtained by forming the piezoelectric thin film 15 with PZT, that is, a metal oxide having a perovskite structure.
- the piezoelectric effect refers to the property of a piezoelectric body in which polarization (and voltage) occurs when stress is applied, or stress and deformation occur when voltage is applied to the piezoelectric film.
- it may be composed of a pyroelectric material that exhibits a pyroelectric effect, or may be composed of a ferroelectric material having memory properties.
- a pyroelectric material is a piezoelectric material that has spontaneous polarization without applying an electric field from the outside. Dielectric polarization (and electromotive force caused by it) in response to a minute temperature change. It has the property that occurs.
- the piezoelectric thin film 15 is composed of a pyroelectric material, the piezoelectric element 1 can be used as an infrared sensor.
- FIG. 3A to FIG. 3E are cross-sectional views showing manufacturing steps of the piezoelectric element 1 of the first embodiment.
- a thermal oxide film 12 is formed on the substrate 11 to a thickness of about 100 nm.
- a single crystal Si wafer having a thickness of about 400 ⁇ m was used as the substrate 11.
- the thermal oxide film 12 is formed by exposing the Si wafer to a high temperature of about 1200 ° C. in an oxygen atmosphere using a wet oxidation furnace.
- a Ti layer 13 'having a thickness of about 20 nm is formed on the thermal oxide film 12 by using a sputtering apparatus.
- the sputtering conditions for Ti at this time are, for example, Ar (argon) flow rate: 27 sccm, pressure: 0.27 Pa, substrate temperature: 145 ° C., RF power applied to the target: 150 W.
- the Ti layer 13 ′ is heated to about 700 ° C. in an oxygen atmosphere to oxidize Ti, and is composed of a TiOx layer.
- the adhesion layer 13 is formed.
- RMS Root Mean Square
- the root mean square roughness RMS is expressed by the following equation (1).
- Ti diffuses into the Pt film when exposed to a high temperature in a subsequent step (for example, formation of a PZT thin film on Pt), and the surface of the Pt layer.
- a hillock may be formed in the PZT, which may cause a leakage of driving current of the PZT and a deterioration of the orientation of the PZT.
- these disadvantages can be prevented by oxidizing Ti to form a TiOx layer as described above.
- the adhesion layer may be formed of a Ti layer instead of the TiOx layer.
- a Pt film is formed on the adhesion layer 13 by sputtering to form a lower electrode 14 having a thickness of 80 nm, for example.
- the sputtering conditions for Pt at this time are, for example, Ar flow rate: 20 sccm, pressure: 0.27 Pa, substrate temperature: 420 ° C., RF power: 150 W.
- a PZT film is formed on the lower electrode 14 by sputtering to form a piezoelectric thin film 15 having a thickness of 4 ⁇ m.
- the sputtering conditions of PZT at this time are Ar flow rate: 25 sccm, O 2 flow rate: 0.8 sccm, substrate temperature: 500 ° C., pressure: 0.4 Pa, RF power: 400 W.
- the piezoelectric element 1 shown in FIG. 1 can be obtained.
- Example 2 the piezoelectric element 1 was manufactured under the same conditions as in Example 1 except that the substrate temperature at the time of film formation of Pt constituting the lower electrode 14 was set to 520 ° C.
- Comparative Example 1 a piezoelectric element was manufactured under the same conditions as in Example 1 except that the substrate temperature at the time of film formation of Pt constituting the lower electrode was 220 ° C.
- Comparative Example 2 a piezoelectric element was manufactured under the same conditions as in Example 1 except that the substrate temperature during deposition of Pt constituting the lower electrode was set to 320 ° C.
- Comparative Example 3 a piezoelectric element was manufactured under the same conditions as in Example 1 except that the substrate temperature at the time of film formation of Pt constituting the lower electrode was 565 ° C.
- each of the lower electrodes formed in Examples 1 and 2 and Comparative Examples 1 to 3 is evaluated by XRD (X-ray Diffraction; X-ray diffraction) before forming a piezoelectric thin film thereon. And surface observation using an AFM (Atomic Force Microscope). The results are shown below.
- Pt or Pt layer refers to Pt (or Pt layer) constituting the lower electrode on the TiOx layer.
- FIG. 4 shows the relationship between the substrate temperature during Pt film formation and the half width of the rocking curve of the (111) plane of Pt in X-ray diffraction.
- the rocking curve is a curve showing an intensity distribution with respect to changes in diffraction conditions. In general, the fuller the crystal, the narrower the half-value width of the curve.
- FIG. 4 shows that the half-value width of the rocking curve decreases as the substrate temperature during the Pt film formation increases.
- FIG. 5 and 6 show the relationship between the substrate temperature during Pt film formation and the surface roughness of the Pt layer measured using AFM, respectively.
- FIG. 5 shows the surface roughness in terms of root mean square RMS (or Rq)
- FIG. 6 shows the surface roughness in terms of arithmetic mean roughness Ra.
- FIG. 7 shows the relationship between the substrate temperature during the Pt film formation and the average value of the Pt particle size measured using the AFM.
- the root mean square roughness RMS and the arithmetic mean roughness Ra are expressed by the following equations.
- the reference length L is extracted from the roughness curve in the direction of the average line
- the direction of the average line in the extracted portion is the x axis
- the direction of the vertical magnification is the y axis.
- the units of y, L, Rms, and Ra are all nm here.
- the rocking curve half-value width of the Pt layer is 2.2 ° or less, and a Pt film having good crystallinity is obtained.
- the piezoelectric thin film 15 with good crystallinity can be formed on the Pt layer.
- the root mean square roughness RMS of the surface of the Pt layer is 1.0 nm or less and the arithmetic average roughness Ra of the surface of the Pt layer is 0.8 nm or less
- the surface of the Pt layer It can be said that the flatness of is good.
- the average particle size of Pt is as large as 200 nm or more.
- FIG. 8 shows a result of evaluation by XRD 2 ⁇ / ⁇ measurement of the PZT film after forming a PZT film as the piezoelectric thin film 15 on the lower electrode 14 of Example 1.
- shaft is shown by the count rate (cps; count per second) of the X-ray per second.
- E + n indicates 1 ⁇ 10 n .
- the crystal structure of the deposited PZT film is (100) / It can be seen that a suitable perovskite crystal structure exhibiting a good piezoelectric effect with (001) plane preferred orientation is obtained.
- FIG. 9 shows a result of evaluation by XRD 2 ⁇ / ⁇ measurement of the PZT film after forming a PZT film as the piezoelectric thin film 15 on the lower electrode 14 of Example 2.
- the peak indicating the (100) / (001) plane appears remarkably, and the peak indicating the (111) plane is low, so the crystal structure of the deposited PZT film is (100) It can be seen that a suitable perovskite crystal structure having a / (001) plane preferred orientation is obtained.
- FIG. 10 shows the results of evaluation by XRD 2 ⁇ / ⁇ measurement of the PZT film after forming a PZT film as a piezoelectric thin film on the lower electrode of Comparative Example 3.
- the peak indicating the (100) / (001) plane is low, while the peak indicating the (110) plane also appears, so that a preferable crystal structure is obtained as the crystal structure of the deposited PZT film. It can be said that it is not.
- FIG. 11 shows the result of evaluation by XRD 2 ⁇ / ⁇ measurement of the PZT film after forming a PZT film as a piezoelectric thin film on the lower electrode of Comparative Example 2.
- the evaluation result for the PZT film of Comparative Example 2 is closer to the result of the Example than the result of Comparative Example 3, but the peak indicating the (111) plane is also more prominent than the peak indicating the (100) / (001) plane. Is not optimal.
- the Pt layer had a rocking curve half-value width of 2.2 ° or less and a surface root mean square roughness RMS of 1.0 nm or less (or surface arithmetic average roughness). Satisfying all the conditions that the average particle diameter of Pt is 200 nm or more, even if the film forming conditions of Pt change within the range satisfying such conditions, A Pt layer having good crystallinity and orientation can be formed, and a Pt layer having good characteristics can be stably formed. As a result, the piezoelectric thin film 15 having good characteristics can be stably formed on the Pt layer.
- the average particle diameter of Pt is as large as 250 nm or more, the columnar crystal of the piezoelectric thin film 15 grows larger on the Pt layer, and the orientation of the piezoelectric thin film 15 is reliably improved.
- the characteristic of the piezoelectric thin film 15 improves reliably.
- the allowable range of fluctuation of the substrate temperature at the time of forming the Pt film becomes narrower from 400 ° C. to 540 ° C. from FIG. 7, but even if the substrate temperature fluctuates within such a range, the characteristic of It can be said that a good piezoelectric thin film 15 can be obtained.
- the piezoelectric element lower electrode described above is a piezoelectric element lower electrode serving as a lower electrode of a piezoelectric thin film formed on a substrate.
- the lower electrode is composed of a Pt layer, and in the Pt layer, X
- the half-value width of the rocking curve of the (111) plane of Pt in line diffraction is 2.2 ° or less
- the root mean square roughness RMS (or Rq) is 1.0 nm or less
- the average grain size of Pt The diameter is 200 nm or more.
- the piezoelectric element lower electrode described above is a piezoelectric element lower electrode which becomes a lower electrode of a piezoelectric thin film formed on a substrate, and the lower electrode is composed of a Pt layer, and in the Pt layer,
- the half-value width of the rocking curve of the (111) plane of Pt in X-ray diffraction is 2.2 ° or less, the arithmetic average roughness Ra of the surface is 0.8 nm or less, and the average particle size of Pt is , 200 nm or more.
- the half-value width of the rocking curve of the (111) plane of Pt is 2.2 ° or less, and the crystallinity of the Pt layer is good. Therefore, the crystallinity of the piezoelectric thin film formed on the Pt layer can be improved.
- a piezoelectric thin film having a suitable crystal structure preferentially oriented in the (100) / (001) plane can be obtained.
- the root mean square roughness RMS of the surface of the Pt layer is 1.0 nm or less, or the arithmetic average roughness Ra of the surface of the Pt layer is 0.8 nm or less, the surface flatness of the Pt layer
- the columnar crystal of the piezoelectric thin film can be grown on the same crystal plane in the film thickness direction from the initial stage of the piezoelectric thin film formation.
- the average particle diameter of Pt is 200 nm or more, the columnar crystal of the piezoelectric thin film can be grown greatly.
- the orientation of the piezoelectric thin film can be improved because the surface roughness of the Pt layer that is the base of the piezoelectric thin film is small and the average particle diameter of Pt is large.
- Pt film formation conditions for example, during film formation
- a Pt layer having good crystallinity and orientation can be formed, and a Pt layer having good characteristics can be stably formed.
- a piezoelectric thin film having good characteristics can be stably formed on the Pt layer.
- the average particle diameter of Pt in the Pt layer is 250 nm or more.
- the columnar crystal of the piezoelectric thin film formed on the Pt layer can be grown larger, and the orientation of the piezoelectric thin film can be reliably improved.
- the piezoelectric element described above is a piezoelectric element in which a lower electrode, a piezoelectric thin film, and an upper electrode are sequentially formed on a substrate, and the lower electrode is composed of the above-described piezoelectric element lower electrode.
- an adhesion layer is formed between the substrate and the lower electrode.
- the adhesion layer By providing the adhesion layer, peeling between the lower electrode and the lower layer can be prevented.
- a TiOx layer is desirable.
- the root mean square roughness RMS of the surface is desirably 2.0 nm or less. Since the surface roughness of the TiOx layer is small and the flatness of the surface is improved, the crystallinity and orientation of Pt of the lower electrode formed on the TiOx layer can be improved.
- a Pt layer having good characteristics can be stably formed by satisfying all the conditions regarding the half-value width of the rocking curve, the average roughness of the surface, and the average particle diameter of the Pt layer. be able to.
- a piezoelectric thin film having good characteristics can be stably formed on the Pt layer.
- a piezoelectric thin film preferentially oriented on the (100) / (001) plane can be formed.
- the present invention can be used for, for example, a MEMS actuator (particularly, an inkjet head actuator), a sensor (thermal sensor, ultrasonic sensor), a frequency filter, and a nonvolatile memory.
- a MEMS actuator particularly, an inkjet head actuator
- a sensor thermo sensor, ultrasonic sensor
- a frequency filter and a nonvolatile memory.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Particle Formation And Scattering Control In Inkjet Printers (AREA)
- Physical Vapour Deposition (AREA)
- General Electrical Machinery Utilizing Piezoelectricity, Electrostriction Or Magnetostriction (AREA)
Abstract
Description
図1は、本実施形態の圧電素子1の概略の構成を示す断面図である。この圧電素子1は、基板11上に、熱酸化膜12と、密着層13と、下部電極14と、圧電薄膜15と、上部電極16とをこの順で形成して構成されている。
次に、上記構成の圧電素子1の製造方法について、実施例1および2として説明する。また、実施例1および2との比較のため、比較例1~3についても併せて説明する。図3(a)~図3(e)は、実施例1の圧電素子1の製造工程を示す断面図である。
まず、図3(a)に示すように、基板11上に熱酸化膜12を100nm程度形成する。ここで、基板11としては、厚さ400μm程度の単結晶Siウェハを用いた。上記の熱酸化膜12は、ウェット酸化用熱炉を用いて上記Siウェハを酸素雰囲気中に1200℃程度の高温にさらすことで形成される。
実施例2では、下部電極14を構成するPtの成膜時の基板温度を520℃とした以外は、実施例1と同じ条件で圧電素子1を作製した。
比較例1では、下部電極を構成するPtの成膜時の基板温度を220℃とした以外は、実施例1と同じ条件で圧電素子を作製した。
比較例2では、下部電極を構成するPtの成膜時の基板温度を320℃とした以外は、実施例1と同じ条件で圧電素子を作製した。
比較例3では、下部電極を構成するPtの成膜時の基板温度を565℃とした以外は、実施例1と同じ条件で圧電素子を作製した。
次に、実施例1~2および比較例1~3で成膜した下部電極のそれぞれについて、その上に圧電薄膜を成膜する前に、XRD(X-ray Diffraction ;X線回折)による評価、およびAFM(Atomic Force Microscope ;原子間力顕微鏡)を用いた表面観察による評価を行った。その結果を以下に示す。なお、以下において、Pt(またはPt層)と記載すれば、TiOx層上の下部電極を構成するPt(またはPt層)を指すものとする。
11 基板
13 密着層
14 下部電極(圧電素子用下部電極)
15 圧電薄膜
16 上部電極
Claims (5)
- 基板上に形成される圧電薄膜の下部電極となる圧電素子用下部電極であって、
該下部電極は、Pt層で構成され、
前記Pt層において、
X線回折におけるPtの(111)面のロッキングカーブの半価幅が、2.2°以下であり、
表面の粗さが、二乗平均粗さRMSが1.0nm以下、及び、算術平均粗さRaが0.8nm以下、のうちの少なくとも一方を満たし、
Ptの平均粒径が、200nm以上であることを特徴とする圧電素子用下部電極。 - 前記Pt層におけるPtの平均粒径が、250nm以上であることを特徴とする請求項1に記載の圧電素子用下部電極。
- 基板上に、下部電極、圧電薄膜および上部電極を順に形成した圧電素子であって、
前記下部電極は、請求項1に記載の圧電素子用下部電極で構成されていることを特徴とする圧電素子。 - 前記基板と前記下部電極との間に、密着層としてのTiOx層が形成されていることを特徴とする請求項3に記載の圧電素子。
- 前記密着層としてのTiOx層の表面の二乗平均粗さRMSが、2.0nm以下であることを特徴とする請求項4に記載の圧電素子。
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EP12790218.7A EP2717344B1 (en) | 2011-05-23 | 2012-05-09 | Lower electrode for piezoelectric element, and piezoelectric element provided with lower electrode |
CN201280025098.5A CN103548164B (zh) | 2011-05-23 | 2012-05-09 | 压电元件用下部电极及具备它的压电元件 |
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JP2014187219A (ja) * | 2013-03-25 | 2014-10-02 | Hitachi Metals Ltd | 圧電体薄膜積層基板 |
JP2014199910A (ja) * | 2013-03-14 | 2014-10-23 | 株式会社リコー | 圧電体薄膜素子及びインクジェット記録ヘッド、並びにインクジェット式画像形成装置 |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1095111A (ja) * | 1996-09-25 | 1998-04-14 | Seiko Epson Corp | 圧電体薄膜素子及びこれを用いたインクジェット式記録ヘッド |
JP2000068454A (ja) | 1998-08-18 | 2000-03-03 | Fuji Electric Co Ltd | 誘電体薄膜コンデンサ |
JP2003017767A (ja) | 2001-07-03 | 2003-01-17 | Sony Corp | 圧電素子 |
JP2004311922A (ja) | 2002-12-24 | 2004-11-04 | Seiko Epson Corp | 電極膜およびその製造方法、ならびに強誘電体メモリおよび半導体装置 |
JP2005198117A (ja) * | 2004-01-09 | 2005-07-21 | Tdk Corp | 電子デバイス作製用構造体及びこれを用いた電子デバイスの製造方法 |
JP2007281238A (ja) | 2006-04-07 | 2007-10-25 | Fujifilm Corp | 圧電素子とその製造方法、及びインクジェット式記録ヘッド |
JP2010161330A (ja) * | 2008-12-08 | 2010-07-22 | Hitachi Cable Ltd | 圧電薄膜素子 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3520403B2 (ja) | 1998-01-23 | 2004-04-19 | セイコーエプソン株式会社 | 圧電体薄膜素子、アクチュエータ、インクジェット式記録ヘッド、及びインクジェット式記録装置 |
JP4240445B2 (ja) * | 2002-05-31 | 2009-03-18 | 独立行政法人産業技術総合研究所 | 超高配向窒化アルミニウム薄膜を用いた圧電素子とその製造方法 |
JP4601896B2 (ja) | 2002-10-30 | 2010-12-22 | 富士通セミコンダクター株式会社 | 半導体装置及びその製造方法 |
US7163828B2 (en) | 2003-03-24 | 2007-01-16 | Seiko Epson Corporation | Electrode, method of manufacturing the same, ferroelectric memory, and semiconductor device |
JP4379475B2 (ja) * | 2004-12-24 | 2009-12-09 | 株式会社村田製作所 | 圧電薄膜共振子およびその製造方法 |
JP5471612B2 (ja) * | 2009-06-22 | 2014-04-16 | 日立金属株式会社 | 圧電性薄膜素子の製造方法及び圧電薄膜デバイスの製造方法 |
-
2012
- 2012-05-09 WO PCT/JP2012/061855 patent/WO2012160972A1/ja active Application Filing
- 2012-05-09 JP JP2013516281A patent/JP5621922B2/ja active Active
- 2012-05-09 CN CN201280025098.5A patent/CN103548164B/zh active Active
- 2012-05-09 EP EP12790218.7A patent/EP2717344B1/en active Active
- 2012-05-09 US US14/119,779 patent/US9331605B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1095111A (ja) * | 1996-09-25 | 1998-04-14 | Seiko Epson Corp | 圧電体薄膜素子及びこれを用いたインクジェット式記録ヘッド |
JP2000068454A (ja) | 1998-08-18 | 2000-03-03 | Fuji Electric Co Ltd | 誘電体薄膜コンデンサ |
JP2003017767A (ja) | 2001-07-03 | 2003-01-17 | Sony Corp | 圧電素子 |
JP2004311922A (ja) | 2002-12-24 | 2004-11-04 | Seiko Epson Corp | 電極膜およびその製造方法、ならびに強誘電体メモリおよび半導体装置 |
JP2005198117A (ja) * | 2004-01-09 | 2005-07-21 | Tdk Corp | 電子デバイス作製用構造体及びこれを用いた電子デバイスの製造方法 |
JP2007281238A (ja) | 2006-04-07 | 2007-10-25 | Fujifilm Corp | 圧電素子とその製造方法、及びインクジェット式記録ヘッド |
JP2010161330A (ja) * | 2008-12-08 | 2010-07-22 | Hitachi Cable Ltd | 圧電薄膜素子 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2717344A4 |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2846370A4 (en) * | 2012-05-01 | 2015-07-08 | Konica Minolta Inc | PIEZOELECTRIC ELEMENT |
JP2014199910A (ja) * | 2013-03-14 | 2014-10-23 | 株式会社リコー | 圧電体薄膜素子及びインクジェット記録ヘッド、並びにインクジェット式画像形成装置 |
JP2014187219A (ja) * | 2013-03-25 | 2014-10-02 | Hitachi Metals Ltd | 圧電体薄膜積層基板 |
JP2015082541A (ja) * | 2013-10-22 | 2015-04-27 | 株式会社リコー | 電気−機械変換素子とその製造方法及び電気−機械変換素子を備えた液滴吐出ヘッド、インクカートリッジ並びに画像形成装置 |
KR20170021292A (ko) * | 2014-06-24 | 2017-02-27 | 울박, 인크 | Pzt 박막적층체 및 pzt 박막적층체의 제조 방법 |
WO2015198882A1 (ja) * | 2014-06-24 | 2015-12-30 | 株式会社アルバック | Pzt薄膜積層体及びpzt薄膜積層体の製造方法 |
JPWO2015198882A1 (ja) * | 2014-06-24 | 2017-04-20 | 株式会社アルバック | Pzt薄膜積層体及びpzt薄膜積層体の製造方法 |
KR102493684B1 (ko) * | 2014-06-24 | 2023-01-31 | 울박, 인크 | Pzt 박막적층체 및 pzt 박막적층체의 제조 방법 |
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JP2018129494A (ja) * | 2017-02-07 | 2018-08-16 | キヤノン株式会社 | 圧電アクチュエータおよびその製造方法、ならびに液体吐出ヘッド |
JP2019048944A (ja) * | 2017-09-11 | 2019-03-28 | Agcコーテック株式会社 | 塗膜、塗膜付き基材およびフッ素系塗料 |
JP7054998B2 (ja) | 2017-09-11 | 2022-04-15 | Agcコーテック株式会社 | 塗膜および塗膜付き基材 |
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JP7423978B2 (ja) | 2019-10-28 | 2024-01-30 | セイコーエプソン株式会社 | 圧電素子、液体吐出ヘッド、およびプリンター |
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