WO2015177948A1 - Film métallique et procédé de formation de film métallique - Google Patents

Film métallique et procédé de formation de film métallique Download PDF

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WO2015177948A1
WO2015177948A1 PCT/JP2015/000086 JP2015000086W WO2015177948A1 WO 2015177948 A1 WO2015177948 A1 WO 2015177948A1 JP 2015000086 W JP2015000086 W JP 2015000086W WO 2015177948 A1 WO2015177948 A1 WO 2015177948A1
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Prior art keywords
film
target
substrate
voltage
specific resistance
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PCT/JP2015/000086
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English (en)
Japanese (ja)
Inventor
和人 山中
池田　真義
隆史 中川
翼 深石
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キヤノンアネルバ株式会社
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Priority to JP2016520906A priority Critical patent/JP6082165B2/ja
Publication of WO2015177948A1 publication Critical patent/WO2015177948A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/14—Structure thereof only for on-demand ink jet heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation

Definitions

  • the present invention relates to a low resistivity metal film formed by sputtering and a film forming method thereof.
  • Ta is often used as a stable and low electrical resistance material in lead wiring used for magnetic heads in semiconductors and storage.
  • Ta is known to have either an ⁇ structure or a ⁇ structure as a crystal structure at room temperature.
  • the ⁇ structure is a body-centered cubic (bcc) structure, and bulk Ta often has an ⁇ structure.
  • bcc body-centered cubic
  • a thin film usually tends to have a ⁇ structure that is a tetragonal structure of a metastable phase.
  • the specific resistance of an ⁇ structure Ta film (also referred to as ⁇ -Ta) is as low as about 13 to 20 ⁇ ⁇ cm, whereas the specific resistance of a ⁇ structure Ta film (also referred to as ⁇ -Ta) is about 170 to 200 ⁇ ⁇ cm. And high. Therefore, it is desirable to use ⁇ -Ta rather than ⁇ -Ta for lead wiring that requires low electrical resistance.
  • a thin Ta film is likely to be ⁇ -Ta.
  • a special treatment is required to turn the thin Ta film into ⁇ -Ta.
  • a semiconductor wiring in order to form a Ta film ( ⁇ -Ta) having an ⁇ structure, TaN is formed as a base layer, and a Ta film is formed thereon.
  • a bcc material is deposited as an underlayer, and a Ta film is deposited thereon.
  • ⁇ -Ta can be formed by forming a predetermined underlayer and then forming a Ta film.
  • ⁇ -Ta for an ink jet type thermal head (recording head) has been studied.
  • a heating resistor that generates bubbles in the ink and wirings that are electrically connected to the heating resistor are formed at a high density on the same substrate.
  • the base of the thermal head is desired to have a structure capable of efficiently generating heat in the heating resistor and at the same time reducing mechanical damage caused by the heat generation and chemical damage caused by ink contact. . Therefore, in a general thermal head substrate, the heating resistor connected to the wiring pattern is covered with a protective film, and the heating resistor conducts heat to the ink through this protective film, and bubbles are formed in the ink. Give rise to
  • the protective film covering the heating resistor is a film that can withstand mechanical or chemical damage, and is required to have insulating properties to protect the wiring. Therefore, the protective film used for conventional general thermal heads is a highly stable upper film that can withstand mechanical damage caused by heat generation and chemical damage caused by ink, and an insulating lower film that protects wiring. Often has a two-layer structure. Specifically, for example, ⁇ -Ta having high chemical and mechanical stability is used for the upper layer film, and a SiN film or SiO film that can be formed relatively easily by an existing semiconductor manufacturing apparatus is used for the lower layer film. It is done.
  • a thermal head substrate using a conventional general two-layer protective film may not have sufficient thermal conductivity, residual stress characteristics, and structural stability.
  • the protective film used for the thermal head is formed thin with a material having high thermal conductivity.
  • the protective film is preferably formed thick. That is, it has been difficult for the conventional protective film to meet these two conflicting requirements.
  • the Ta film includes an ⁇ structure Ta film ( ⁇ -Ta) and a ⁇ structure Ta film ( ⁇ -Ta).
  • ⁇ -Ta is used in a conventional general two-layer protective film, it is more suitable to use ⁇ -Ta having an ⁇ structure having a low specific resistance, that is, a high thermal conductivity.
  • ⁇ -Ta film forming methods Several methods have been proposed as ⁇ -Ta film forming methods.
  • a TiW film is formed on the entire surface of ⁇ -Ta previously formed by sputtering using a mask other than the portion corresponding to the heat generating portion. Thereafter, TiW and the mask are etched, and ⁇ -Ta is obtained by causing phase transition of at least part of ⁇ -Ta corresponding to the heat generating portion.
  • ⁇ -Ta is formed by performing sputtering while introducing a small amount of nitrogen gas.
  • ⁇ -Ta is formed by sputtering Ta on a base film made of at least one element selected from an element group having a bcc crystal structure.
  • JP 2008-302625 A JP 2006-517614 Japanese Patent Laid-Open No. 11-120525
  • Patent Document 1 includes a certain degree of variation in the accuracy of the arrangement of the formed mask. If the difference between the position of the formed mask and the position of the heat generating portion is large, there is a problem that the high thermal conductivity of ⁇ -Ta cannot function effectively.
  • Patent Document 2 has a problem that process management is difficult because it is necessary to control a small amount of nitrogen gas pressure.
  • ⁇ -Ta but also ⁇ -Ta is partially generated, or nitrogen gas and Ta react to generate TaN, so that the specific resistance of the obtained film may not be as expected. is there.
  • the present invention has been made in view of the above-described technical problems, and has high thermal conductivity and structural stability that can be easily formed at a high yield at a low yield by a manufacturing process that is simplified compared to the prior art.
  • An object of the present invention is to provide a metal film having the same and a film forming method thereof.
  • a first aspect of the present invention is a film forming method for forming a Ta film on a substrate by sputtering, wherein VHF power and a first DC voltage are applied to the Ta target, and the Ta target is sputtered. 1 and Ta atoms sputtered from the Ta target in the first step are deposited on the substrate maintained at a first temperature to form a Ta film having a specific resistance of 60 ⁇ ⁇ cm or less. And a second step of forming a film.
  • a second aspect of the present invention is a Ta film, in which a VHF power and a first DC voltage are applied to a Ta target, the Ta target is sputtered, and the Ta step is performed in the first step. And having a specific resistance of 60 ⁇ ⁇ cm or less formed by the second step of depositing Ta atoms sputtered from the target on the substrate maintained at the first temperature.
  • a Ta film having a low specific resistance of 60 ⁇ ⁇ cm or less is formed by applying VHF power and a first DC voltage to a Ta target and performing sputtering, without forming a mask or an underlayer. ( ⁇ -Ta) can be formed.
  • FIG. 1 is a schematic configuration diagram of a film forming apparatus 100 according to the present embodiment.
  • the film forming apparatus 100 includes a vacuum container 101 (chamber) to which an exhaust unit 102 such as a vacuum pump and a gas introduction unit 103 such as a mass flow controller (MFC) are connected.
  • a gate valve 101a is provided on the side wall of the vacuum vessel 101.
  • the vacuum vessel 101 can be sealed by closing the gate valve 101a, and the substrate S is opened via the gate valve 101a by opening the gate valve 101a. Can be carried in and out.
  • a cathode 104 cathode electrode
  • a substrate stage 105 on which a substrate S can be placed at a position facing the cathode 104 are provided.
  • the cathode 104 is connected to a VHF power source 107 via a matching unit 106 and also connected to a superimposing DC power source 108.
  • the frequency of the VHF power source 107 is 60 MHz.
  • the frequency of the VHF power source 107 is not limited to this value, and may be any high frequency from 20 MHz to 450 MHz.
  • a magnet mechanism 104a is provided in the cathode.
  • the magnet mechanism 104a is a PCM (Point Cusp Magnet).
  • the PCM includes a large number of magnet pieces provided on a plate-like support, and each magnet piece has the same shape and the same magnetic flux density.
  • the magnet pieces are arranged in a grid pattern at substantially the same intervals. Any two adjacent magnet pieces have opposite polarities when viewed from the target T side. On the other hand, in the quadrangle formed of any four adjacent magnet pieces, the polarities of the two magnet pieces along the diagonal direction viewed from the target T side are the same. With such an arrangement, a point cusp magnetic field is formed by any four adjacent magnet pieces.
  • the magnet mechanism 104a When PCM is used as the magnet mechanism 104a, the magnetic field strength on the surface of the target T is increased, and thereby the discharge impedance can be kept low. In addition, the magnetic field strength greatly decreases with distance from the target T, and a sufficiently weak magnetic field is formed in the vicinity of the substrate S, so that the influence of Ar ions on the substrate can be reduced.
  • the magnet mechanism 104a is not limited to PCM, and an arbitrary shape such as a flat plate shape or a rod shape and an arbitrary number of magnets may be used.
  • the substrate stage 105 includes a heating mechanism (not shown) connected to the heating power source 109 and a high temperature ESC (electrostatic adsorption) device (not shown) connected to the ESC power source 110.
  • the substrate stage 105 is further connected to a bias power source 111 via a matching unit (not shown).
  • the frequency of the bias power supply 111 is 13.56 MHz.
  • the shield 112 is configured so that part or all of the side walls can be driven.
  • a predetermined VHF power from the VHF power source 107 and a predetermined DC voltage from the DC power source 108 are made of Ta via the cathode 104.
  • the target T is sputtered.
  • Ta atoms sputtered from the target T are deposited on the substrate S held at a predetermined temperature on the substrate stage 105 to form a Ta film.
  • the film forming process was performed under various conditions as follows, and various measurements were performed on the formed film.
  • Example 1 As Example 1 according to this embodiment, a film forming process was performed under the following conditions. First, the Ta target T was fixed to the cathode 104 by bonding, and the substrate S was placed on the substrate stage 105. As the substrate S, a 300 mm thermal oxide film substrate was used. The thermal oxide film of the substrate S is 100 nm, and its surface is an insulator.
  • the substrate S on the substrate stage 105 was heated to 370 ° C.
  • Ar gas for processing was introduced from the gas introduction unit 103 at a flow rate of 100 sccm, and the pressure in the vacuum vessel 101 was set to 5 Pa.
  • 500 W of 60 MHz VHF power was applied to the cathode 104 to start discharging.
  • the discharge voltage at this time is ⁇ 10 V or less, and is a potential at which sputtering hardly occurs.
  • the pressure in the vacuum vessel 101 is increased to 0.4 Pa below the ignition limit by adjusting the conductance valve of the exhaust unit 102 and increasing the exhaust speed without changing the Ar gas flow rate in a state where discharge is continued. Lowered. Thereafter, the VHF power applied to the cathode 104 was set to 1500 W, and a DC voltage of ⁇ 50 V was superimposed on the cathode 104 to form a film for a predetermined time.
  • an ESC voltage of ⁇ 600 V was applied to the substrate stage 105, and Ar gas for heat conduction was introduced to the back surface of the substrate S. In this embodiment, no bias voltage is applied to the substrate stage 105.
  • Comparative Example 1 As Comparative Example 1, a film forming process was performed under the following conditions. The temperature of the substrate S was room temperature (20 ° C.), the pressure in the vacuum vessel 101 was the same 2 Pa before and after discharge, the VHF power was 2000 W, and the DC voltage was ⁇ 300 V. The other conditions were the same as those in Example 1 for film formation.
  • Comparative Example 2 As Comparative Example 2, the film was formed under the same conditions as in Example 1 except that the DC voltage was ⁇ 200V.
  • the film thickness was measured by the X-ray reflectivity measurement method (XRR), and the sheet resistance was measured by a sheet resistance measuring instrument using a direct current 4-probe method, and the specific resistance value of the formed film was calculated.
  • the crystal structure of the formed film was examined using an out-of-plane measurement by X-ray diffraction (XRD). The crystal grain size was observed with a planar TEM, and the grain size in the formed film was analyzed.
  • Example 1 In the measurement results of Example 1, it was confirmed that the film thickness was 80 nm and the specific resistance was 16 ⁇ ⁇ cm, which is as low as the bulk. The crystal grain size (average equivalent circle diameter or average particle size) at this time was ⁇ 257 nm. On the other hand, in the measurement result of Comparative Example 1, the specific resistance was 170 ⁇ ⁇ cm at a film thickness of 32 nm, which was about 10 times higher than that of Example 1. The crystal grain size at this time was ⁇ 8 nm. In the measurement result of Comparative Example 2, the specific resistance was 143 ⁇ ⁇ cm, and the specific resistance was also about 10 times higher than Example 1.
  • FIGS. 2A and 2B are diagrams showing the XRD measurement results of Example 1 and Comparative Examples 1 and 2.
  • FIG. 2A the horizontal axis is the angle, and the vertical axis is the intensity.
  • the graph of E1 shows the measurement result of Example 1
  • the graph of C1 shows the measurement result of Comparative Example 1
  • the graph of C2 shows the measurement result of Comparative Example 2.
  • FIG. 2B is a diagram showing the peak position with respect to the angle for Example 1 (E1) and Comparative Example 1 (C1) of FIG. 2A.
  • Example 1 (E1) in FIG. 2A a peak indicating the (110) plane of ⁇ -Ta having a bcc structure was strongly observed around 38.5 degrees. That is, it was confirmed that an ⁇ -Ta film can be formed by the film forming method according to this embodiment.
  • FIG. 3 is a diagram showing changes in orientation and half width (FWHM) when measurement is performed while changing only the VHF power among the conditions of Example 1.
  • the horizontal axis in FIG. 3 is the VHF power, and the vertical axis is the orientation and the full width at half maximum (FWHM).
  • FIG. 4 is a diagram showing changes in specific resistance and film formation rate when measurement is performed by changing only the VHF power among the conditions of Example 1.
  • FIG. The horizontal axis in FIG. 4 is the VHF power
  • the vertical axis is the specific resistance (Resistability) and the deposition rate (Deposition Rate).
  • an arrow attached to each graph indicates which vertical axis the graph corresponds to.
  • FIG. 3 represents the ratio of the peak intensity of the (110) plane to the peak intensity of the (200) plane of the XRD measurement result. A large value of this orientation indicates that the content of ⁇ -Ta which is a bcc structure in the Ta film is high.
  • the half width in FIG. 3 is calculated from the peak width of the XRD measurement result, and indicates the degree of variation in crystal spacing (lattice spacing). It is known that the larger the half width, the smaller the crystal grain size, and the smaller the crystal grain size, the greater the specific resistance. In FIG. 3, the full width at half maximum tends to decrease as the VHF power increases, and it was found that increasing the VHF power increases the crystal grain size.
  • the film formation rate can be increased while keeping the specific resistance low. That is, when the VHF power is increased, Ar ions increase and the cathode current increases. As a result, the cathode power increases even when the absolute value of the cathode voltage is kept low, so that the deposition rate can be increased.
  • the film forming conditions for obtaining ⁇ -Ta were investigated.
  • the measurement result of the Ta structure formed when the conditions are variously changed on the basis of the film formation conditions of the above-described Example 1 will be described.
  • the specific resistance increased as the film thickness decreased from 80 nm, and the specific resistance of the 20 nm film became equal to the specific resistance of ⁇ -Ta.
  • the ratio of ⁇ -Ta tends to increase, and at ⁇ 300 V, the deposited film is ⁇ - It became Ta single phase.
  • FIGS. 5 and 6 are diagrams showing whether or not ⁇ -Ta can be obtained for each combination of film thickness, DC voltage, and substrate temperature.
  • FIG. 5 shows the results of measurement performed by forming a Ta film having a thickness of 70 nm
  • FIG. 6 shows the results of measurement performed by forming a Ta film having a thickness of 30 nm.
  • a Ta film having a low specific resistance of 60 ⁇ ⁇ cm or less is considered to be a phase having a high ⁇ -Ta content.
  • a circle indicates a combination with a specific resistance of 60 ⁇ ⁇ cm or less
  • a triangle indicates a specific resistance of 60 ⁇ ⁇ cm or less due to film formation pressure, bias voltage conditions, or adjustment of the stage configuration.
  • the x mark is a combination having a specific resistance larger than 60 ⁇ ⁇ cm.
  • the conditions for ⁇ -Ta at a film thickness of 70 nm are that the film forming temperature is 300 ° C. or higher and the DC voltage is ⁇ 150 V or higher.
  • the conditions for ⁇ -Ta at a film thickness of 30 nm are that the film formation temperature is 370 ° C. or higher and the DC voltage is ⁇ 100 V or higher.
  • the higher the temperature and the higher the DC voltage that is, the smaller the absolute value
  • ⁇ -Ta having a low resistance can be obtained by increasing the thickness of the film if the film forming conditions are at least a film forming temperature of 300 ° C. and a DC voltage of ⁇ 150 V or higher.
  • the absolute value of the DC voltage (cathode voltage) on the target side is kept smaller than the general sputtering condition, so that Ar ions are used as a target in a state where acceleration due to cathode fall is low. Incident. For this reason, it is considered that the recoil Ar reflected from the target surface has a low speed and is less likely to enter the film formed on the substrate. As a result, it is considered that Ar entering into the film is reduced and ⁇ -Ta having a bcc structure and a small specific resistance is easily generated.
  • the effect of making Ar difficult to enter the film by reducing the absolute value of the DC voltage (cathode voltage) and slowing the recoil Ar is not limited to Ta, but has a large content of Ar such as W or Au. It is considered that the wiring material having a relatively large mass number appears similarly. That is, even with these materials, it is considered that a film having a low specific resistance can be obtained by the film forming conditions for slowing the recoil Ar as in the case of Ta. A specific resistance film could be obtained.
  • the film forming speed is impaired because high-density plasma is generated by the VHF power.
  • ⁇ -Ta having a low specific resistance can be formed.
  • the film forming method according to the present embodiment uses 60 MHz VHF power rather than 13.56 MHz RF, the number of oscillations of electrons in the plasma increases. Since the electrons collide with Ar gas in the gas phase and Ar ions are generated, more Ar ions can be generated at a high frequency, and high-density plasma can be obtained.
  • the deposition rate is proportional to the product of the DC voltage (cathode voltage) and the cathode current (cathode power).
  • the absolute value of the DC voltage is reduced in order to suppress recoil Ar, a large amount of Ar ions are generated because the discharge is performed with VHF having a higher frequency than in the past. A lot of cathode current flows. Therefore, it is possible to form ⁇ -Ta without preventing a decrease in cathode power and without deteriorating the film formation speed.
  • Vdc is generated, so it seems that the specific resistance is low to some extent.
  • the absolute value of Vdc is larger than when VHF power of 60 MHz is applied. Therefore, ⁇ -Ta and ⁇ are included in the formed Ta film. It is considered difficult to obtain a film in which —Ta is mixed and the resistivity is sufficiently low.
  • a general DC cathode generates a discharge voltage of minus several hundred volts, so it is considered that a film having a low specific resistance cannot be obtained.
  • the absolute value of Vdc generated at the cathode can be kept low by using the VHF power source.
  • the film forming method according to the present embodiment it is possible to directly form ⁇ -Ta without forming a mask or an underlayer as in the prior art, so that film formation can be performed at a lower cost than in the past. it can.
  • the film formation process can be simplified, the yield can be improved.
  • a Ta film having better thermal conductivity, residual stress characteristics, structural stability, and the like can be formed.
  • Example 1 the specific resistance between ⁇ -Ta formed on TaN as the underlayer and ⁇ -Ta formed under the conditions of this embodiment (Example 1) was compared.
  • the specific resistance of ⁇ -Ta formed in (1) was lower. This is probably because ⁇ -Ta formed on TaN has a smaller crystal grain size than ⁇ -Ta formed in Example 1. Therefore, according to the film forming method according to the present embodiment, ⁇ -Ta having better characteristics than the conventional technique in which a Ta film is formed on a base layer made of TaN can be obtained.
  • Examples of the substrate on which ⁇ -Ta can be formed by the film forming method according to this embodiment include a silicon substrate on which a silicon oxide film is formed, a substrate on which an SiN insulating protective layer is formed, and a silicon substrate.
  • the ⁇ -Ta film forming method according to the present embodiment is suitably used for forming a Ta film required in a thermal head for an ink jet printer or a semiconductor wiring process requiring a low specific resistance film. It can also be used to form a lead wiring for a magnetic head.
  • the film forming method according to this embodiment is useful.
  • ⁇ -Ta formed by the film forming method according to the present embodiment is more stable with respect to temperature because it does not require a TaN layer and does not need to contain nitrogen as compared with the conventional method. Therefore, durability becomes high.
  • Vdc which is a DC voltage
  • Vdc a DC voltage
  • ⁇ -Ta having a low specific resistance
  • Vdc at the time of film formation was ⁇ 20 V
  • the specific resistance was 16.3 ⁇ ⁇ cm. Therefore, it has been found that ⁇ -Ta can also be obtained by generating Vdc at the cathode 104 by VHF power without supplying a DC voltage from the external power source to the cathode 104.
  • Example 1 Under the conditions of Example 1 according to the first embodiment, the pressure in the vacuum vessel 101 was changed from 5 Pa to 0.4 Pa before and after the discharge, but this change was not made and the measurement was performed at 5 Pa before and after the discharge. At this time, VHF power was set to 2000 W, bias power of 100 W was applied to the substrate S from the bias power supply 111, and other conditions were the same as the film forming conditions of Example 1. As a result, ⁇ -Ta could be obtained as in Example 1. Therefore, it has been found that ⁇ -Ta can be obtained by applying a DC voltage having a small absolute value above a predetermined temperature regardless of the conditions of pressure and bias power.
  • FIG. 7 is a diagram showing the relationship between film thickness and specific resistance.
  • the horizontal axis in FIG. 7 is the film thickness of the formed Ta film, and the vertical axis is the specific resistance.
  • FIG. 7 shows experimental results when the film forming temperatures are 360 ° C. and 400 ° C. From FIG. 7, at both 360 ° C. and 400 ° C., a decrease in specific resistance is observed at a film thickness of 20 nm or more, and ⁇ -Ta crystallinity can be obtained. More preferably, when the film thickness is 30 nm or more, the resistivity is sufficiently low (that is, 60 ⁇ ⁇ cm or less), and ⁇ -Ta is obtained.
  • the first film is formed under the film formation conditions of Example 1 at a predetermined thickness where an ⁇ -Ta film is formed, and then the film formation rate is high.
  • ⁇ -Ta is formed at a high film formation rate. More specifically, after the first film is formed under the film formation conditions of the DC voltage of ⁇ 150 V or more and the film formation temperature of 300 ° C. or more, the DC voltage is less than ⁇ 150 V and the film formation temperature on the first film. A second film is formed under film formation conditions of less than 300 ° C.
  • the laminated Ta film of the first film and the second film formed as a whole has an ⁇ -Ta structure.
  • the film formation rate is lower than that in the ⁇ -Ta film formation condition.
  • the ⁇ -Ta film forming condition for which a sufficient film forming speed cannot be obtained is combined with the ⁇ -Ta film forming condition having a high film forming speed. -Improve puts.
  • the Ta film formed as the second film may be formed using a film formation method different from that in Example 1 and Comparative Examples 1 and 2, and in a separate processing chamber in consideration of productivity. It may be done.
  • the internal stress (residual stress near the surface) of ⁇ -Ta produced in Example 1 according to the first embodiment was tensile stress.
  • the internal stress of the laminated Ta film produced by the film forming method according to the present embodiment was a compressive stress. Therefore, by forming a laminated Ta film by the film forming method according to this embodiment, it is possible to control the internal stress of the film while maintaining the ⁇ -Ta crystallinity. In general, it is more advantageous in terms of corrosion resistance, fatigue strength, etc. that the stress on the surface of the film is a compressive stress. Therefore, ⁇ -Ta formed by the film forming method according to the present embodiment has a low specific resistance and a compressive stress on the surface, and thus functions such as corrosion resistance and life are further improved.
  • This embodiment is a method for manufacturing an inkjet thermal head to which the ⁇ -Ta film forming method according to any of the first to fourth embodiments is applied.
  • a thermal head (recording head) is a component that ejects ink of an inkjet printer toward a sheet, an ink chamber that stores ink, an ink supply chamber that supplies ink to the ink chamber, and an ejection port that ejects ink from the ink chamber.
  • a bubble generating unit that heats the ink in the ink chamber to generate bubbles in the ink.
  • the thermal head is configured to extrude ink by bubbles generated by heating a part of the ink at a bubble generation unit in the ink chamber, and to discharge the ink from the discharge port toward the paper.
  • the bubble generating unit includes a heating unit having a heating element, and the surface of the heating unit is covered with a protective layer provided on the inner wall of the ink chamber. Since the bubble generating part is in direct contact with the ink, it may be corroded by the ink. Therefore, the protective layer covering the heating part surface of the bubble generating part is exposed to chemical stability (corrosion resistance), high thermal conductivity (low specific resistance), heat resistance, and repeated thermal expansion and contraction. It is required to have high fatigue strength (mechanical stability). As a protective layer having these properties, ⁇ -Ta having a low specific resistance is suitable.
  • FIG. 8 is a cross-sectional view of the periphery of the bubble generating portion of the thermal head 900 manufactured by the manufacturing method according to the present embodiment.
  • the thermal head 900 includes a heat storage layer 902 made of SiO 2 , a heating resistor layer 903 made of TaN, an electrode layer 904 made of Al, an insulating protective layer 905 made of SiN, and a substrate 901 made of Si.
  • a protective layer 906 made of -Ta is sequentially formed.
  • the material of each layer is an example, and any material may be used as long as the function of the thermal head can be ensured.
  • a SiO 2 film as a heat storage layer 902 as a base of a heating resistor is formed on a substrate 901 by a thermal oxidation method, a sputtering method, a CVD method, or the like.
  • a TaN film as the heating resistor layer 903 is formed on the heat storage layer 902 by a sputtering method.
  • an Al film as an electrode layer 904 is formed on the heating resistor layer 903 by a sputtering method.
  • a predetermined portion of the heating resistor layer 903 and the electrode layer 904 is etched to partition an electrode pattern and a heating area having a predetermined shape.
  • the heating region can be heated by passing a current through the heating region (heating resistor layer 903) through the electrode pattern (electrode layer 904) thus formed.
  • a SiN film as an insulating protective layer 905 is formed by a thermal oxidation method, a sputtering method, a CVD method, or the like. Thereafter, ⁇ -Ta as the protective layer 906 is formed on the insulating protective layer 905 by the film forming method according to any of the first to fourth embodiments.
  • ⁇ -Ta is directly formed without the need for forming a mask or a base film before forming ⁇ -Ta as in the prior art. Can do. Therefore, it is possible to manufacture a thermal head having a protective film with a low specific resistance at a lower cost than before. Since the manufacturing process can be simplified, the yield can be improved. In addition, it is possible to provide a thermal head substrate that has higher performance than conventional ones, and to realize a thermal head capable of maintaining a high-frequency discharge operation in a stable state for a long period of time.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Physical Vapour Deposition (AREA)
  • Particle Formation And Scattering Control In Inkjet Printers (AREA)
  • Electrodes Of Semiconductors (AREA)

Abstract

　La présente invention, dans un mode de réalisation, concerne un procédé de formation de film, comprenant une première étape d'application d'une puissance VHF à partir de l'alimentation VHF (107) et une première tension continue à partir d'une alimentation en courant continu (108) à une cible en Ta (T) et de pulvérisation cathodique de la cible en Ta (T) et une seconde étape de dépôt d'atomes de Ta, pulvérisés à partir de la cible en Ta dans la première étape, sur un substrat (S) qui est maintenu à une première température sur une platine (105) pour substrat et de formation d'un film de Ta ayant une résistance spécifique inférieure ou égale à 60 μΩ・cm.
PCT/JP2015/000086 2014-05-22 2015-01-09 Film métallique et procédé de formation de film métallique WO2015177948A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001335919A (ja) * 2000-03-21 2001-12-07 Murata Mfg Co Ltd αタンタル膜の製造方法、αタンタル膜及びそれを用いた素子
JP2002124600A (ja) * 2000-10-17 2002-04-26 Sharp Corp 配線基板およびその製造方法
JP2011516728A (ja) * 2008-04-03 2011-05-26 オーシー オリコン バルザース エージー スパッタリング装置および金属化構造体を製造する方法
JP2013538295A (ja) * 2010-09-17 2013-10-10 アプライド マテリアルズ インコーポレイテッド 高アスペクト比特徴部に金属を堆積させる方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001335919A (ja) * 2000-03-21 2001-12-07 Murata Mfg Co Ltd αタンタル膜の製造方法、αタンタル膜及びそれを用いた素子
JP2002124600A (ja) * 2000-10-17 2002-04-26 Sharp Corp 配線基板およびその製造方法
JP2011516728A (ja) * 2008-04-03 2011-05-26 オーシー オリコン バルザース エージー スパッタリング装置および金属化構造体を製造する方法
JP2013538295A (ja) * 2010-09-17 2013-10-10 アプライド マテリアルズ インコーポレイテッド 高アスペクト比特徴部に金属を堆積させる方法

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