WO2009081992A1 - 反射電極、表示デバイス、および表示デバイスの製造方法 - Google Patents
反射電極、表示デバイス、および表示デバイスの製造方法 Download PDFInfo
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- WO2009081992A1 WO2009081992A1 PCT/JP2008/073655 JP2008073655W WO2009081992A1 WO 2009081992 A1 WO2009081992 A1 WO 2009081992A1 JP 2008073655 W JP2008073655 W JP 2008073655W WO 2009081992 A1 WO2009081992 A1 WO 2009081992A1
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- alloy layer
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- display device
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- reflective electrode
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- 239000000758 substrate Substances 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
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- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims description 113
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- 238000004544 sputter deposition Methods 0.000 claims description 66
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
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- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 6
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- 229910052689 Holmium Inorganic materials 0.000 claims description 6
- 229910052771 Terbium Inorganic materials 0.000 claims description 6
- 229910052775 Thulium Inorganic materials 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
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- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 59
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 21
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract 1
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- 230000015572 biosynthetic process Effects 0.000 description 27
- 239000004973 liquid crystal related substance Substances 0.000 description 24
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- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
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- 238000012986 modification Methods 0.000 description 4
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
- G02B5/0825—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only
- G02B5/0833—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only comprising inorganic materials only
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133553—Reflecting elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133553—Reflecting elements
- G02F1/133555—Transflectors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
Definitions
- the present invention relates to a reflective electrode used in a display device typified by a liquid crystal display or an organic electroluminescence (EL) display, a display device including the reflective electrode, and a method for manufacturing the same.
- a liquid crystal display will be described as a representative example, but the present invention is not limited to this.
- liquid crystal displays There are two types of liquid crystal displays: transmissive display devices that use light from a lighting device (backlight) installed behind the liquid crystal panel as a light source, reflective display devices that use ambient light, and both transmissive and reflective types.
- the display device is roughly classified into a semi-transmission type display device having both functions.
- the transmissive display device performs display by passing the backlight irradiated from the rear surface of the liquid crystal panel through the liquid crystal panel and the color filter, and displays a high contrast ratio regardless of the use environment. It has the advantage of being capable of being used, and is widely used in electronic devices that require large brightness such as televisions and personal computer monitors. However, since power for the backlight is required, it is somewhat unsuitable for small devices such as mobile phones.
- Reflective display devices on the other hand, reflect natural light or artificial light within a liquid crystal panel and display the reflected light through a liquid crystal panel or color filter. It is widely used mainly for calculators and watches.
- the reflective display device has a drawback in that the brightness and contrast ratio of the display are greatly affected by the use environment, and in particular, it becomes difficult to see when it becomes dark.
- transflective display devices use reflective electrodes during the day to save power consumption, and light and turn on lights when necessary indoors or at night, depending on the usage environment.
- the display device in the transmissive mode and the display in the reflective mode can be performed, there is an advantage that power consumption can be saved without being restricted by the surrounding environment, and a bright high contrast ratio display can be obtained.
- the transflective display device is optimally used for mobile devices, and in particular, is widely used for colored mobile phones and the like.
- FIGS. 1 and 2 the configuration and operation principle of a typical transflective liquid crystal display device will be described. 1 and FIG. 2 correspond to FIG. 1 and FIG. 2 disclosed in Patent Document 3 described later.
- a transflective liquid crystal display device 11 includes a thin film transistor (hereinafter referred to as TFT) substrate 21, a counter substrate 15 disposed to face the TFT substrate 21, and a TFT substrate. 21 and a counter substrate 15, and a liquid crystal layer 23 that functions as a light modulation layer.
- the counter substrate 15 includes a color filter 17 including a black matrix 16, and a transparent common electrode 13 is formed on the color filter 17.
- the TFT substrate 21 has a pixel electrode 19, a switching element T, and a wiring portion including a scanning line and a signal line. In the wiring portion, a plurality of gate wirings 5 and a plurality of data wirings 7 are arranged perpendicular to each other, and a switching element TFT (in the figure, T) are arranged in a matrix.
- the pixel region P of the pixel electrode 19 is composed of a transmissive region A and a reflective region C.
- the transmissive region A is a transparent electrode (pixel electrode) 19 a
- the reflective region C is a transparent electrode.
- 19a and a reflective electrode 19b are provided.
- a barrier metal layer 51 made of a refractory metal such as Mo, Cr, Ti, W is formed between the transparent electrode 19a and the reflective electrode 19b (details will be described later).
- the operation principle of the transmission mode will be described.
- the light F of the backlight 41 disposed below the TFT substrate 21 is used as a light source.
- the light emitted from the backlight 41 enters the liquid crystal layer 23 through the transparent electrode 19a and the transmission region A, and the alignment of liquid crystal molecules in the liquid crystal layer 23 is caused by an electric field formed between the transparent electrode 19a and the common electrode 13.
- the direction is controlled, and the incident light F from the backlight 41 passing through the liquid crystal layer 23 is modulated.
- the amount of light transmitted through the counter substrate 15 is controlled to display an image.
- external natural light or artificial light B is used as a light source.
- the light B incident on the counter substrate 15 is reflected by the reflective electrode 19b, and the alignment direction of the liquid crystal molecules in the liquid crystal layer 23 is controlled by the electric field formed between the reflective electrode 19b and the common electrode 13.
- the passing light B is modulated.
- the amount of light transmitted through the counter substrate 15 is controlled to display an image.
- the pixel electrode 19 includes a transparent electrode 19a and a reflective electrode 19b.
- the transparent electrode 19a is typically indium tin oxide (ITO) containing about 10% by mass of tin oxide (SnO) in indium oxide (In 2 O 3 ), or 10% of zinc oxide in indium oxide. % Of oxide conductive film such as indium zinc oxide (IZO).
- the reflective electrode 19b is made of a metal material having a high reflectance, and typically, an Al alloy such as pure Al or Al—Nd (hereinafter collectively referred to as an Al-based alloy) is used. It has been. Since Al has a low electrical resistivity, it is extremely useful as a wiring material.
- a refractory metal barrier metal layer 51 such as Mo is formed between the Al-based alloy thin film constituting the reflective electrode 19b and the oxide conductive film such as ITO or IZO constituting the transparent electrode.
- the reason for forming is that when these are directly connected to form a reflective region, the contact resistance increases due to galvanic corrosion or the like, and the display quality of the screen decreases. That is, Al is very easily oxidized, and there is a large difference in electrode potential between the pure Al and the oxide conductive film in the alkaline electrolyte (developer) (the electrode potential of pure Al is ⁇ 1.9 V).
- the electrode potential of ITO is ⁇ 0.17 V.
- Patent Documents 1 to 3 a barrier metal layer such as Mo or Cr is interposed between an Al-based alloy layer and a transparent pixel electrode (ITO or the like) based on such a viewpoint.
- the contact resistance value is reduced.
- the characteristics required for the wiring material constituting the reflective electrode include high reflectivity and low electrical resistivity of the wiring material itself.
- the reflectivity of refractory metals such as Mo and Cr is very low. Therefore, for example, when the reflection region is configured by reflection at the interface between the transparent pixel electrode and the Al-based alloy layer, in order to display in the reflection mode, the barrier metal layer is purposely removed and the Al-based alloy layer is intentionally removed. It was necessary to be exposed.
- the wiring material constituting the reflective electrode has the above characteristics after heat treatment even if film formation is performed under a low heat treatment of about 100 to 300 ° C., for example, with the recent decrease in film formation temperature. It is also required to be excellent (high reflectivity, low electrical resistivity, low contact resistance) and to have excellent heat resistance that does not generate hillocks (cove-like projections) on the wiring surface.
- the process temperature when manufacturing display devices tends to decrease further from the viewpoint of yield improvement and productivity, etc. With recent improvements in film formation technology, film formation at about 250 ° C. is possible, for example. It is because of.
- the transflective display device has been described as an example.
- the request described above is not limited to this, and is generally required for a display device having a reflective region for displaying in a reflective mode.
- the present invention has been made paying attention to the above circumstances, and the object thereof is to provide an oxide conductive layer in which a metal layer (Al alloy thin film) constituting a reflective electrode constitutes a transparent electrode without interposing a barrier metal layer.
- a reflective electrode directly connected to a film which has a high reflectance and a low contact resistance value even when subjected to a low heat treatment of, for example, about 100 ° C. or more and 300 ° C. or less, and has defects such as hillocks.
- An object of the present invention is to provide a reflective electrode excellent in heat resistance that does not occur, and to provide a display device including the reflective electrode and a manufacturing method thereof.
- the reflective electrode of the present invention that has solved the above problems is a reflective electrode for a display device formed on a substrate, and the reflective electrode is at least one of 0.1 to 2 atomic% of Ni and Co.
- X is La, Mg, Cr, Mn, Ru, Rh, Pt, Pd, Ir, Ce, Pr, Gd, Tb, Dy, Nd, Ti, Zr, 1st Al containing at least one element selected from the group consisting of Nb, Mo, Hf, Ta, W, Y, Fe, Sm, Eu, Ho, Er, Tm, Yb, and Lu.
- [O] / which is the ratio of the number of O atoms to the number of Al atoms in the second Al oxide layer Al] is 0.30 or less
- the thickness of the thinnest portion of the second Al oxide layer is 10 nm or less
- the reflective electrode includes the second Al oxide layer and the transparent pixel electrode.
- the present invention has a gist where it is formed between the transparent pixel electrode and the substrate.
- the first Al— (Ni / Co) —X alloy layer includes at least one of 0.1 to 2 atomic% of Ni and Co, 0.1 to 2 atomic% of La, Containing.
- the first Al— (Ni / Co) —X alloy layer includes 0.1 to 2 atomic% of Ni and at least one of 0.1 to 2 atomic% of La and Nd; Containing.
- the first Al— (Ni / Co) —X alloy layer further includes 0.1 to 2 atomic% of Z (Z is selected from the group consisting of Ge, Cu, and Si). Contains a kind of element.
- the first Al— (Ni / Co) —X alloy layer includes at least one of 0.1 to 2 atomic% of Ni and Co, 0.1 to 2 atomic% of La, 0.1 to 2 atomic% of Ge and Cu.
- the first Al— (Ni / Co) —X alloy layer includes 0.1 to 2 atomic% of Ni and at least one of 0.1 to 2 atomic% of La and Nd; 0.1 to 2 atomic% of Ge and Cu.
- the transparent pixel electrode described above is preferably at least one of indium tin oxide (ITO) and indium zinc oxide (IZO).
- the present invention includes a display device including any of the reflective electrodes described above.
- the display device provided with the reflective electrode of the present invention described above can be manufactured by the following three methods.
- an Al—Ni—X alloy layer or an Al— (Ni / Co) —X alloy layer is formed on a substrate by sputter deposition, and the formed Al—Ni—X alloy layer or Al
- the step of heat-treating the-(Ni / Co) -X alloy layer at a temperature of 200 ° C. or higher in a vacuum or an inert gas atmosphere and the step of forming a transparent pixel electrode by sputter deposition are sequentially included. Has a gist.
- an Al—Ni—X alloy layer or an Al— (Ni / Co) —X alloy layer is formed on a substrate by sputter deposition, and the formed Al—Ni—X alloy layer or Al is formed.
- a step of forming a transparent pixel electrode on a (Ni / Co) -X alloy layer by sputter deposition, wherein the sputter deposition is performed in a deposition atmosphere containing a nitrogen component at least in the initial stage of the sputter deposition. are included in order.
- a third manufacturing method includes a step of forming an Al—Ni—X alloy layer or an Al— (Ni / Co) —X alloy layer on a substrate by sputter deposition, and the formed Al—Ni—X alloy layer or Al.
- the present invention is summarized in that it includes a step of reverse sputtering the-(Ni / Co) -X alloy layer and a step of forming a transparent pixel electrode by sputter deposition.
- the Al—Ni—X alloy layer or the Al— (Ni / Co) —X alloy layer further contains 0.1 to 2 atomic% of Z (Z is Ge, Cu And at least one element selected from the group consisting of Si).
- the reflective electrode of the present invention since there is a small Al oxide layer and a small amount of O (oxygen) in the contact region with the transparent pixel electrode, the reflective electrode can be used without a barrier metal layer as in the prior art. Even if the Al oxide layer constituting the electrode is directly connected to the oxide conductive film constituting the transparent electrode, it is excellent in all properties such as reflection characteristics, contact resistance, electrical resistivity, and heat resistance. Specifically, for example, even when a low heat treatment of about 100 ° C. or higher and 300 ° C. or lower is performed, the film has high reflectivity and low contact resistance, and does not cause defects such as hillocks. Therefore, when the reflective electrode of the present invention is used, a display device with excellent productivity, low cost, and high performance can be provided.
- O oxygen
- FIG. 1 is an exploded perspective view showing a configuration of a typical transflective liquid crystal display device.
- FIG. 2 is a diagram schematically showing a cross section of a typical transflective liquid crystal display device.
- FIG. 3 is a cross-sectional view of an essential part of a display device including the reflective electrode of the present invention.
- 4 shows the sample No. of Example 1.
- 27 is a transmission electron micrograph showing the interface between the reflective electrode of No. 27 (Example of the present invention, with heat treatment) and the ITO film.
- 5 shows the sample No. of Example 1.
- 2 is a transmission electron micrograph showing an interface between a reflective electrode of No. 2 (comparative example, no heat treatment) and an ITO film.
- FIG. 1 is an exploded perspective view showing a configuration of a typical transflective liquid crystal display device.
- FIG. 2 is a diagram schematically showing a cross section of a typical transflective liquid crystal display device.
- FIG. 3 is a cross-sectional view of an
- FIG. 6 is a graph showing changes in reflectance of various reflective electrodes immediately after film formation.
- FIG. 7 is a graph showing changes in reflectance of various reflective electrodes after vacuum heating at 200 ° C.
- FIG. 8 is a graph showing changes in reflectance of various reflective electrodes after vacuum heating at 220 ° C.
- FIG. 9 is a graph showing changes in reflectance of various reflective electrodes after vacuum heating at 250 ° C.
- TFT Barrier metal layer T Switching element
- the inventors of the present invention exhibit excellent reflection characteristics even if a barrier metal layer is not interposed between the oxide conductive film constituting the transparent pixel electrode and the metal thin film constituting the reflective electrode. Furthermore, in order to provide a reflective electrode excellent in characteristics such as contact resistance and electric resistivity as well as maintaining good reflection characteristics even when subjected to low-temperature heat treatment, it has been studied earnestly. .
- Al—Ni—X alloy containing 2 atomic% the heat resistance can be improved (iii) or the Si— and / or Ge elements (hereinafter, for convenience of explanation) can be added to the Al—Ni—X alloy.
- Group Z. 0.1 to 2 atomic% With that Al-Ni-X-Z alloy, reflectance, contact resistance, properties such as heat resistance and we found that is further improved.
- an Al oxide layer (AlO x , x ⁇ 0.30) containing less oxygen than Al 2 O 3 (AlO 1.5 ) and having a small thickness (thickness of the thinnest portion ⁇ 10 nm)
- AlO x , x ⁇ 0.30 containing less oxygen than Al 2 O 3 (AlO 1.5 ) and having a small thickness (thickness of the thinnest portion ⁇ 10 nm)
- a reflective electrode having a contact resistance value lower than that of a conventional Al alloy layer can be obtained by forming the Al—Ni—X alloy layer on the Al—Ni—X alloy layer.
- Co may be used instead of Ni, and Co has been found to be an effective element having the same action as Ni.
- the alloy layer may contain a group Z element (Si and / or Ge), but it has also been found that the group Z may further contain Cu. That is, the alloy layer may further contain 0.1 to 2 atomic% of group Z (group Z is at least one element selected from the group consisting of Ge, Cu, and Si). As a result, it has also been found that the contact resistance reducing action is further enhanced.
- an Al alloy containing Ni and / or Co and at least one group X may be referred to as an Al— (Ni / Co) —X alloy.
- an Al alloy further including at least one of group Z in the Al— (Ni / Co) —X alloy may be referred to as an Al— (Ni / Co) —XZ alloy.
- these Al alloys are sometimes collectively referred to as Al— (Ni / Co) —X— (Z) alloys.
- an Al oxide layer (AlO x , x ⁇ 0.30, thickness of the thinnest portion ⁇ 10 nm) containing less oxygen and the thinnest portion is formed of Al— (Ni / Co).
- the contact resistance value can be reduced by forming it on the -X- (Z) alloy layer.
- AlO x , x> 0.30, the thickness of the thinnest portion> 10 nm) having a high contact resistance due to a large amount of oxygen and a large film thickness is considered to be inhibited.
- the present invention is not limited to such an estimation mechanism.
- “high reflectance” or “excellent in reflection characteristics” means that when the reflectance immediately after film formation and after heat treatment is measured by the method described in the examples described later, It means that the reflectance at 550 nm is 90% or more.
- low contact resistance means that when the contact resistance immediately after film formation and after heat treatment is measured by the method described in the examples described later (100 ⁇ square contact hole), It means that the contact resistance is 1 k ⁇ or less. The lower the contact resistance, the better, and the preferred contact resistance is about 500 ⁇ or less, more preferably about 100 ⁇ or less.
- the reflective electrode of the present invention includes the first Al— (Ni / Co) —X alloy layer 2a and the second Al oxide layer 2b containing Al and O (oxygen). Yes.
- the second Al oxide layer 2 b is directly connected to the transparent pixel electrode 3.
- the reflective electrode of the present invention is formed between the transparent pixel electrode 3 and the substrate 1 in a region where the second Al oxide layer 2b and the transparent pixel electrode 3 are directly connected.
- the reflective electrode of the present invention has an Al oxide layer (second layer) with little oxygen and a thinnest part on an Al- (Ni / Co) -X alloy layer (first layer). It is characterized by being. That is, the layer of the reflective electrode directly connected to the transparent pixel electrode is not the Al— (Ni / Co) —X alloy layer that is the first layer, but the Al oxide layer that is the second layer.
- [O] / [Al] which is a ratio of the number of O atoms to the number of Al atoms in the Al oxide layer, is 0.30 or less, preferably It is 0.25 or less, more preferably 0.20 or less.
- the thickness of the thinnest part of the Al oxide layer is 10 nm or less, preferably 8 nm or less, more preferably 6 nm or less.
- the total amount of (Ni, Co) in the Al— (Ni / Co) —X alloy layer is 0.1 atomic% or more (preferably 0.3). Atomic% or higher, more preferably 0.5 atomic% or higher) and 2 atomic% or lower (preferably 1.5 atomic% or lower, more preferably 1.0 atomic% or lower).
- X in the first Al— (Ni / Co) —X alloy layer is La, Mg, Cr, Mn, Ru, Rh, Pt, Pd, Ir, Ce, Pr, Gd, Tb, Dy, Nd, and Ti. , V, Zr, Nb, Mo, Hf, Ta, W, Y, Fe, Sm, Eu, Ho, Er, Tm, Yb and at least one element selected from the group consisting of Lu. All of these are useful as heat resistance improving elements, and the formation of hillocks (cove-like projections) on the surface of the Al-based alloy thin film is effectively prevented.
- the content of X is less than 0.1 atomic%, the heat resistance improving effect cannot be exhibited effectively.
- the X content is preferably as high as possible.
- the upper limit exceeds 2 atomic%, the electrical resistivity of the Al— (Ni / Co) —X alloy film itself increases. . Therefore, considering the reduction of electrical resistivity and the effect of improving heat resistance, the content of X is preferably 0.2 atomic% or more and 0.8 atomic% or less.
- These elements may be added alone or in combination of two or more. When two or more elements are added, the total content of each element may be controlled so as to satisfy the above range.
- Al— (Ni / Co) —X alloy layer 0.1 to 2 atomic% of Ni and / or Co, 0.1 to 2 atomic% of La and / or Nd, Most preferably, an alloy layer containing is used.
- the balance of the Al— (Ni / Co) —X alloy layer is substantially composed of Al and inevitable impurities.
- the Al— (Ni / Co) —X alloy layer is further at least one element selected from the group consisting of 0.1 to 2 atomic% Z (Z is Ge, Cu, and Si). This may further improve contact resistance, electrical resistivity, and heat resistance.
- the Z content is preferably 0.2 atomic percent or more and 0.8 atomic percent or less.
- Each element of Ge, Cu, and Si belonging to Z may be added alone or in combination of two or more. When two or more elements are added, the total amount of each element may be controlled so as to satisfy the above range.
- Ge and Cu are preferable from the viewpoint of improving the contact resistance with the transparent conductive film. If Ge and Cu are used, the alkali resistance is further improved. Therefore, in the present invention, as the Al— (Ni / Co) —XZ alloy layer, 0.1 to 2 atomic% of Ni and / or Co and 0.1 to 2 atomic% of La and / or Nd are used. It is most preferable to use an alloy layer containing 0.1 to 2 atomic% of Ge and / or Cu.
- the transparent pixel electrode includes indium tin oxide (ITO) (for example, indium oxide (In 2 O 3 ) containing about 10% by mass of tin oxide (SnO)), and / or indium oxide.
- ITO indium tin oxide
- IZO Zinc
- ITO is particularly preferable.
- the reflective electrode of the present invention can be manufactured by the first to third methods described in detail below.
- the formed Al—Ni—X alloy layer is formed after the formation of the Al—Ni—X alloy layer (step I) and before the formation of the transparent pixel electrode (step II). It is characterized in that a heat treatment step is separately provided (step A).
- the second and third manufacturing methods do not perform the heat treatment (step A).
- the transparent pixel electrode is formed.
- the deposition atmosphere is controlled (step IIa).
- the formed Al—Ni—X alloy layer is characterized by reverse sputtering (step B).
- the Al— (Ni / Co) —X alloy layer may be the Al— (Ni / Co) —XZ alloy layer described above.
- Al— (Ni / Co) —X— (Z) alloy layer are collectively abbreviated as “Al— (Ni / Co) —X— (Z) alloy layer”.
- the 1st manufacturing method of this invention is: Forming an Al— (Ni / Co) —X— (Z) alloy layer on the substrate by sputter deposition (step I); Heat-treating the formed Al— (Ni / Co) —X— (Z) alloy layer at a temperature of 200 ° C. or higher in a vacuum or an inert gas atmosphere (step A); Forming a transparent pixel electrode by sputter deposition (step II); Are included sequentially.
- an Al— (Ni / Co) —X— (Z) alloy layer (first layer) is formed by sputter deposition.
- the film formation method by sputter deposition is not particularly limited, and is not particularly limited as long as it is a method usually used for forming an Al alloy film or the like.
- the pressure is approximately 2 mmTorr in a vacuum atmosphere or an inert atmosphere.
- the substrate temperature is preferably controlled within the range of room temperature to about 250 ° C.
- the thickness of the Al alloy film is preferably about 50 to 300 nm.
- the Al— (Ni / Co) —X— (Z) alloy layer (first layer) formed in the above step I is heat-treated at a temperature of 200 ° C. or higher in a vacuum or an inert gas atmosphere.
- This heat treatment is a step characterizing the first manufacturing method of the present invention, and thereby, a desired second Al oxide layer (an Al oxide layer having a small amount of oxygen and a thinnest thickness) can be obtained. It is done. As demonstrated in the examples described later, if the heat treatment is omitted or the heat treatment temperature is removed, the desired second layer cannot be obtained and the contact resistance is lowered.
- Examples of the inert gas used for the heat treatment include N 2 and Ar gas. Only 1 type may be used for an inert gas and it may use 2 or more types together.
- the heat treatment temperature is 200 ° C. or more (preferably 250 ° C. or more), 400 ° C. or less (preferably 350 ° C. or less), and the heat treatment time is 0.5 hours or more (preferably 1 hour or more), 3.5 It is not longer than time (preferably not longer than 3 hours). If the heat treatment temperature is too low or the time is too short, the amount of oxygen in the Al oxide layer and the thickness of its thinnest portion increase. On the other hand, if the heat treatment temperature is too high or the time is too long, the formation of (bump-shaped projections) on the surface of the Al-based alloy thin film increases.
- a transparent pixel electrode is formed by sputter deposition.
- the sputter deposition conditions may be a known appropriate method depending on the type of transparent pixel electrode used.
- an ITO film having a pressure of about 1 mm Torr and a substrate temperature of about room temperature to about 250 ° C. is generally set to about 50 to 300 nm in a vacuum atmosphere or an inert atmosphere such as Ar. It is preferable to form a film.
- the second production method of the present invention comprises: Forming an Al— (Ni / Co) —X— (Z) alloy layer on the substrate by sputter deposition (step I); Forming a transparent pixel electrode on the formed Al- (Ni / Co) -X- (Z) alloy layer by sputter deposition, in a vapor deposition atmosphere containing a nitrogen component in the initial stage of the sputter deposition; A step of performing sputter deposition (step IIa); Are included sequentially.
- the transparent pixel electrode is formed by sputter deposition instead of performing the heat treatment step (step A) characterizing the first manufacturing method. It is characterized by controlling the vapor deposition atmosphere (particularly, the atmosphere at the initial stage of sputter deposition) in the forming process (process II).
- step I the details of the step of forming the Al— (Ni / Co) —X— (Z) alloy layer by sputtering deposition (step I) are the same as those of the first manufacturing method described above.
- a transparent pixel electrode is formed by sputter deposition on the Al— (Ni / Co) —X— (Z) alloy layer formed in step I.
- a nitrogen component preferably Is sputter deposition in a deposition atmosphere containing N 2 gas.
- the second manufacturing method is characterized in that the transparent pixel electrode forming step by sputter deposition is carried out by appropriately controlling the vapor deposition atmosphere. Conditions other than the above-mentioned vapor deposition atmosphere are usually employed sputter vapor deposition conditions. Just do it.
- the amount of oxygen in the Al oxide layer (second layer) can be reduced by including a nitrogen component in the vapor deposition atmosphere.
- a nitrogen component in the vapor deposition atmosphere Normally, as described in the section of (Process II) in the first manufacturing method, an ITO film or the like that forms a transparent pixel electrode is formed in an inert gas atmosphere such as Ar. When the transparent pixel electrode is formed in a gas atmosphere, the desired second layer cannot be obtained, and the contact resistance is lowered (see Examples described later). The reason for this is unknown in detail, but according to the present invention, the nitrogen component-containing ITO film (ITO-N film) formed in the initial film formation stage becomes a so-called barrier layer. It is assumed that interdiffusion between Al and O (oxygen) during heat treatment is suppressed.
- the “initial stage of sputter deposition” means a stage where the oxide transparent conductive film constituting the transparent pixel electrode is formed to a thickness of about 1/5 to 1/2.
- the thickness of the ITO film is about 50 nm, it means a stage in which about 10 to 25 nm is formed.
- all stages of sputter deposition are performed in a deposition atmosphere containing a nitrogen component.
- the “nitrogen component” is preferably N 2 gas. When N 2 gas is used, the amount is preferably 5 to 25% (more preferably 12 to 18%) in terms of the volume flow ratio of sputtering gas to Ar.
- the third production method of the present invention comprises: Forming an Al— (Ni / Co) —X— (Z) alloy layer on the substrate by sputter deposition (step I); A step of reverse sputtering the formed Al— (Ni / Co) —X— (Z) alloy layer (step B); Forming a transparent pixel electrode by sputter deposition (step II); Are included sequentially.
- the heat treatment step (step A) characterizing the first manufacturing method is not performed. Further, in the third manufacturing method, unlike the second manufacturing method, after the formation of the Al— (Ni / Co) —X— (Z) alloy layer (step I) and before the formation of the transparent pixel electrode (step II). Further, the (Ni / Co) —X— (Z) alloy layer formed is characterized by reverse sputtering (step B).
- step I a step of forming an Al— (Ni / Co) —X— (Z) alloy layer by sputter deposition
- step II a step of forming a transparent pixel electrode by sputter deposition
- the Al— (Ni / Co) —X— (Z) alloy layer (first layer) obtained in the step I is subjected to reverse sputtering.
- reverse sputtering means that the voltage applied to the target side electrode and the substrate side electrode in normal sputter deposition is reversed, and ionized inert gas (for example, Ar ions) is not collided with the target. It means impingement on the Al— (Ni / Co) —X— (Z) alloy layer on the substrate.
- the Al oxide layer formed on the Al— (Ni / Co) —X— (Z) alloy layer is removed, and a clean Al—Ni—La alloy layer is formed.
- the amount of oxygen in the Al oxide layer (second layer) can be reduced.
- mutual diffusion of Al and O (oxygen) at the interface can be prevented, and contamination on the surface of the alloy layer can also be removed.
- the reverse sputtering conditions are, for example, in a vacuum atmosphere or an inert atmosphere such as Ar, the pressure is approximately 1 mmTorr, the power is approximately in the range of 10 to 100 W, the substrate temperature Is preferably controlled at room temperature to 250 ° C.
- the present invention includes a display device including the above-described reflective electrode.
- FIG. 3 an example of principal part sectional drawing of the display device provided with the reflective electrode 2 of this invention is shown.
- the reflective electrode 2 of the present invention is formed between the transparent pixel electrode 3 and the substrate 1 in a region where the second Al oxide layer 2b and the transparent pixel electrode 3 are directly connected. ing.
- An insulating film or the like may exist between the reflective electrode 2 and the substrate 1. 3 is shown as one embodiment of the present invention, and the display device of the present invention is not limited to the embodiment of FIG.
- Example 1 In this example, the first manufacturing method described above was studied.
- an Al—Ni—La alloy layer as a reflective electrode material was formed on the surface by sputtering deposition.
- the sputter deposition conditions were an Ar atmosphere, a pressure of 1 mTorr, and a power of 100 W.
- the thickness of the Al—Ni—La alloy layer was about 100 nm.
- Table 1 shows the amounts of Ni and La in the Al—Ni—La alloy layer.
- the Al—Ni—La alloy layer was divided into a layer subjected to heat treatment and a layer not subjected to heat treatment.
- the heat treatment was performed at a temperature shown in Table 1 for 1 hour in a vacuum atmosphere (degree of vacuum ⁇ 3 ⁇ 10 ⁇ 4 Pa) or N 2 atmosphere.
- an untreated and heat-treated Al—Ni—La alloy layer was patterned by photolithography and etching, and an ITO film was formed thereon by sputtering deposition.
- the sputter deposition conditions were an Ar atmosphere, a pressure of 1 mTorr, and a power of 100 W.
- the thickness of the ITO film was about 50 nm.
- the sample No. 1 was heat-treated at a temperature of 200 ° C. or higher in a vacuum or an inert gas (nitrogen) atmosphere.
- a vacuum or an inert gas (nitrogen) atmosphere In 13 to 21 and 25 to 33, an Al oxide layer having an [O] / [Al] ratio of 0.30 or less and a thickness of the thinnest part of 10 nm or less is formed, and 100 ⁇ / cm 2 or less ( The contact resistance value of 70 ⁇ / cm 2 or less was exhibited in the inventive example of Example 1.
- the heat-treated sample No. 27 (Example of the present invention, FIG. 4) is a sample No. that has not been heat-treated.
- the Al oxide layer (AlO x ) is smoother than that of 2 (Comparative Example, FIG. 5). This is because the interdiffusion of Al and O (oxygen) during ITO film formation was inhibited by the formation of an Al oxide layer having an [O] / [Al] ratio of 0.30 or less. Conceivable.
- Example 2 In this example, the second manufacturing method described above was studied.
- Example 2 Specifically, in the same manner as in Example 1, an Al—Ni—La alloy layer (thickness: about 100 nm) and an ITO film (thickness: about 50 nm) are formed on an alkali-free glass plate (thickness: 0.7 mm). Formed. However, unlike Example 1, no heat treatment was performed. Instead, 12% N 2 gas was added in a volume flow rate ratio to the sputtering gas Ar to form an ITO film to obtain a sample of the present invention. For comparison, a sample of a comparative example in which the ITO film was formed only in an Ar gas atmosphere was also prepared.
- the contact resistance value, the [O] / [Al] ratio of the Al oxide layer, and the thickness of the thinnest part were measured in the same manner as in Example 1.
- the thickness of the thinnest part of the oxide layer (second layer) was 8 nm, and the [O] / [Al] ratio was Was 0.15, and the contact resistance value was 50 to 70 ⁇ / cm 2 .
- the thickness of the thinnest part of the oxide layer (second layer) was 18 nm, and [O] / [Al] The ratio was 0.35, and the contact resistance value was 500 to 800 ⁇ / cm 2 .
- Example 3 In this example, the above-described third manufacturing method was examined.
- Example 2 Specifically, in the same manner as in Example 1, an Al—Ni—La alloy layer (thickness: about 100 nm) and an ITO film (thickness: about 50 nm) are formed on an alkali-free glass plate (thickness: 0.7 mm). Formed. However, unlike Example 1, no heat treatment was performed. Instead, after placing the sample in the sputter deposition apparatus for ITO film, Ar gas was introduced, and the surface of the sample was reverse sputtered with Ar for 10 seconds while changing the polarity of sputtering. The reverse sputtering conditions were an Ar atmosphere, a pressure of 1 mm Torr, and a power of 100 W.
- the reverse sputtering conditions were an Ar atmosphere, a pressure of 1 mm Torr, and a power of 100 W.
- Example 2 Thereafter, the polarity of sputtering was returned, and an ITO film was formed in the same manner as in Example 1 to obtain a sample of the present invention. For comparison, a sample of a comparative example in which reverse sputtering was not performed was also prepared.
- the contact resistance value, the [O] / [Al] ratio of the Al oxide layer, and the thickness of the thinnest part were measured in the same manner as in Example 1.
- the thickness of the thinnest part of the oxide layer (second layer) is 7 nm, the [O] / [Al] ratio is 0.17, and the contact resistance value Is 40-80 ⁇ / cm 2 Met.
- the thickness of the thinnest portion of the oxide layer (second layer) was 18 nm, and the [O] / [Al] ratio was 0.55.
- the contact resistance value was 2000 to 2800 ⁇ / cm 2 .
- Example 4 In this example, the following samples in Table 1 that differ only in the amount of Ni were used. These are all examples of the present invention manufactured by the first manufacturing method of the present invention.
- Al-0.5% Ni-0.10% La No. 22 (heat treatment temperature 150 ° C.), No. 25 (heat treatment temperature 200 ° C.), No. 25 28 (heat treatment temperature 250 ° C)
- Al-1.0% Ni-0.35% La As an example of Al-1.0% Ni-0.35% La, No. 23 (heat treatment temperature 150 ° C.), no. 26 (heat treatment temperature 200 ° C.), No. 29 (heat treatment temperature 250 ° C)
- Al-2.0% Ni-0.35% La No. 24 (heat treatment temperature 150 ° C.), 27 (heat treatment temperature 200 ° C.), No. 30 (heat treatment temperature 250 ° C)
- the reflectance immediately after film formation (before heat treatment) and the reflectance after vacuum heating (heating at 200 ° C., 220 ° C., 250 ° C. for 30 minutes) were compared.
- the reflectance was measured using a visible / ultraviolet spectrophotometer “V-570” manufactured by JASCO Corporation in the measurement wavelength range of 1000 to 250 nm.
- V-570 visible / ultraviolet spectrophotometer manufactured by JASCO Corporation
- FIGS. 6 to 9 show changes in reflectance (wavelength: 850 to 250 nm) of each sample immediately after film formation, after vacuum heating at 200 ° C., after vacuum heating at 220 ° C., and after vacuum heating at 250 ° C., respectively. It is a graph. Taking the reflectance at 550 nm as a reference, all of the above samples satisfying the requirements of the present invention had a reflectance at 550 nm of more than 85% to around 90%, both immediately after film formation and after vacuum heating. It had good reflection characteristics.
- the present embodiment is a modification of the first embodiment, in which an Al—Ni—La—Cu alloy layer is used as the Al alloy layer. Specifically, in place of using the Al—Ni—La alloy layer having the composition shown in Table 1 in Example 1, an Al—Ni—La—Cu alloy layer having the composition shown in Table 2 was used, and the heat treatment shown in Table 2 was performed. Each sample of the reflective electrode was produced in the same manner as in Example 1 except that the above was performed. Next, in the same manner as in Example 1, the contact resistance value, the thickness of the thinnest portion of the Al oxide layer, and the ratio of oxygen to Al ([O] / [Al] ratio) were determined. These results are summarized in Table 2.
- the sample No. 2 was heat-treated at a temperature of 200 ° C. or higher in a vacuum or an inert gas (nitrogen) atmosphere. 4-12 and no.
- an Al oxide layer having an [O] / [Al] ratio of 0.30 or less and a thickness of the thinnest part of 10 nm or less was formed.
- the contact resistance value of any sample was about 60 ⁇ / cm 2 or less, and the contact resistance could be kept low.
- the present embodiment is a further modification of the first embodiment, and is an example in which an Al— (Ni / Co) —La—Ge alloy layer (Ge includes 0 atomic%) is used as the Al alloy layer.
- the composition of the Al alloy is set to show the effect of adding Ge in particular, and the content of (Ni / Co) is 0.2 atomic%, which is within the scope of the present invention (0.1 to 0.1%).
- the effect of Ge addition (specifically, a further action of reducing the contact resistance value) in the case where it was set to a low level although it was 2 atomic%) was examined.
- the Al—Ni—La alloy layer having the composition shown in Table 1 in Example 1 instead of using the Al—Ni—La alloy layer having the composition shown in Table 1 in Example 1 above, the Al—Ni—La—Ge alloy layer or Al—Co—La—Ge alloy having the composition shown in Table 3 is used.
- Each sample of the reflective electrode was prepared in the same manner as in Example 1 except that the alloy layer (Ge included 0 atomic% in any alloy layer) was used and the heat treatment shown in Table 3 was performed.
- “Ni / Co” indicates that either Ni or Co was added.
- sample No. 2 was heat-treated at a temperature of 200 ° C. or higher in a vacuum or inert gas (nitrogen) atmosphere. 6-20 and no.
- an Al oxide layer having an [O] / [Al] ratio of 0.30 or less and a thickness of the thinnest part of 10 nm or less is formed.
- These contact resistance values were 1000 ⁇ / cm 2 or less at the maximum, indicating a low contact resistance value.
- the reflective electrode of the present invention since there is a small Al oxide layer and a small amount of O (oxygen) in the contact region with the transparent pixel electrode, the reflective electrode can be used without a barrier metal layer as in the prior art. Even if the Al oxide layer constituting the electrode is directly connected to the oxide conductive film constituting the transparent electrode, it is excellent in all properties such as reflection characteristics, contact resistance, electrical resistivity, and heat resistance. Specifically, for example, even when a low heat treatment of about 100 ° C. or higher and 300 ° C. or lower is performed, the film has high reflectivity and low contact resistance, and does not cause defects such as hillocks. Therefore, when the reflective electrode of the present invention is used, a display device with excellent productivity, low cost, and high performance can be provided.
- O oxygen
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Abstract
Description
透過モードでは、TFT基板21の下部に配置されたバックライト41の光Fを光源として使用する。バックライト41から出射した光は、透明電極19aおよび透過領域Aを介して液晶層23に入射し、透明電極19aと共通電極13との間に形成される電界によって液晶層23における液晶分子の配列方向が制御され、液晶層23を通過するバックライト41からの入射光Fが変調される。これにより、対向基板15を透過する光の透過量が制御されて画像が表示される。
2a 第1の層(Al-Ni-La合金層)
2b 第2の層(Al酸化物層:AlOx、x≦0.30)
2 反射電極
3 透明画素電極(ITOなど)
5 ゲート配線
7 データ配線
8 ゲート電極
9 ソース電極
10 ドレイン電極
11 半透過型液晶表示装置
13 共通電極
15 対向基板
16 ブラックマトリックス
17 カラーフィルター
19 画素電極
19a 透明電極(画素電極)
19b 反射電極
21 TFT基板
23 液晶層
24 ソース領域
25 ドレイン領域
26 チャネル層
27 ゲート絶縁膜
51 バリアメタル層
T スイッチング素子(TFT)
本発明の第1の製造方法は、
基板上に、スパッタ蒸着によってAl-(Ni/Co)-X-(Z)合金層を形成する工程(工程I)と、
形成したAl-(Ni/Co)-X-(Z)合金層を、真空または不活性ガス雰囲気下で200℃以上の温度で熱処理する工程(工程A)と、
スパッタ蒸着によって透明画素電極を形成する工程(工程II)と、
を順次、包含している。
まず、スパッタ蒸着によってAl-(Ni/Co)-X-(Z)合金層(第1の層)を形成する。スパッタ蒸着による成膜方法は特に限定されず、Al合金膜などの成膜に通常用いられる方法であれば特に限定されないが、例えば、真空雰囲気や不活性雰囲気下にて、圧力をおおむね、2mmTorr程度、基板温度を室温~約250℃の範囲内に制御することが好ましい。Al合金膜の厚さは、おおむね、50~300nmの程度にすることが好ましい。
次に、上記の工程Iによって形成したAl-(Ni/Co)-X-(Z)合金層(第1の層)を、真空または不活性ガス雰囲気下で200℃以上の温度で熱処理する。この熱処理は、本発明の第1の製造方法を特徴付ける工程であり、これにより、所望とする第2のAl酸化物層(酸素が少なく、最薄部の厚みが薄いAl酸化物層)が得られる。後記する実施例で実証したように、熱処理を省略したり熱処理温度が外れると、所望とする第2の層が得られず、接触抵抗が低下する。
最後に、スパッタ蒸着によって透明画素電極を形成する。スパッタ蒸着の条件は使用する透明画素電極の種類に応じ、公知の適切な方法を採用すれば良い。例えばITOを成膜する場合は、真空雰囲気やArなどの不活性雰囲気下にて、圧力をおおむね、1mmTorr程度、基板温度をおおむね室温~250℃に制御し、おおむね、50~300nm程度のITO膜を成膜することが好ましい。
本発明の第2の製造方法は、
基板上に、スパッタ蒸着によってAl-(Ni/Co)-X-(Z)合金層を形成する工程(工程I)と、
形成したAl-(Ni/Co)-X-(Z)合金層上にスパッタ蒸着によって透明画素電極を形成する工程であって、前記スパッタ蒸着の初期段階において、窒素成分を含有する蒸着雰囲気中でスパッタ蒸着を行う工程(工程IIa)と、
を順次、包含している。
次に、工程Iによって形成したAl-(Ni/Co)-X-(Z)合金層上にスパッタ蒸着によって透明画素電極を形成するが、ここでは、スパッタ蒸着の初期段階において、窒素成分(好ましくはN2ガス)を含有する蒸着雰囲気中でスパッタ蒸着を行う。第2の製造方法では、スパッタ蒸着による透明画素電極の形成工程を、蒸着雰囲気を適切に制御して実施したところに特徴があり、上記蒸着雰囲気以外の条件は、通常用いられるスパッタ蒸着条件を採用すれば良い。
本発明の第3の製造方法は、
基板上に、スパッタ蒸着によってAl-(Ni/Co)-X-(Z)合金層を形成する工程(工程I)と、
形成したAl-(Ni/Co)-X-(Z)合金層を逆スパッタする工程(工程B)と、
スパッタ蒸着によって透明画素電極を形成する工程(工程II)と、
を順次、包含している。
ここでは、工程Iによって得られたAl-(Ni/Co)-X-(Z)合金層(第1の層)を逆スパッタする。本発明において逆スパッタとは、通常のスパッタ蒸着におけるターゲット側電極および基板側電極に印加する電圧を逆にして、イオン化された不活性ガス(例えばArイオン)を、ターゲットに衝突させるのではなく、基板上のAl-(Ni/Co)-X-(Z)合金層に衝突させることを意味する。このような逆スパッタによってAl-(Ni/Co)-X-(Z)合金層上に形成されたAl酸化物層が除去され、清浄なAl-Ni-La合金層が形成される。そして清浄なAl-Ni-La合金層上に透明画素電極をスパッタ蒸着によって成膜することによって、Al酸化物層(第2の層)中の酸素量を低下させることができる。これにより、界面でのAlとO(酸素)の相互拡散を防止できるほか、合金層表面のコンタミも除去することができる。
本実施例では、前述した第1の製造方法について検討した。
上記のようにして形成した反射電極の試料に、フォトリソグラフィーおよびエッチングによって、接触抵抗測定パターン(接触エリア:20、40、80μm□)を形成した後、窒素雰囲気で177℃(450K)×1時間の熱処理を行った後、接触抵抗値を四端子ケルビン法で測定した。結果を表1に示す。
(1)表1の試料No.2(熱処理無し)およびNo.27(N2雰囲気下200℃で
熱処理)の第1の層(Al-2.0原子%Ni-0.35原子%La合金層)とITO膜との界面を、透過型電子顕微鏡(日立製作所製、型名:HF2000)で観察して、Al酸化物層の最薄部の厚みを求めた(観察領域:約10um、観察倍率:15万倍)。さらにこれら試料のAl酸化物層の組成を、電子励起型特性X線分析によって測定した。これらの結果を、表1、並びに図4および5に示す。
(2)残りの試料(表1の試料No.2および27以外のもの)のAl酸化物層の組成([O]/[Al]比)および最薄部の厚みを、X線光電子分光法(XPS)によって測定した。結果を表1に示す。
本実施例では、前述した第2の製造方法について検討した。
本実施例では、前述した第3の製造方法について検討した。
であった。これに対して逆スパッタを行わなかった比較例の試料では、酸化物層(第2の層)の最薄部の厚みは18nmであり、[O]/[Al]比は0.55であり、接触抵抗値は2000~2800μΩ/cm2であった。
本実施例では、Ni量のみが異なる表1の下記試料を用いた。これらは全て、本発明の第1の製造方法で製造した本発明例である。
・Al-0.5%Ni-0.10%Laの例として、No.22(熱処理温度150℃)、No.25(熱処理温度200℃)、No.28(熱処理温度250℃)
・Al-1.0%Ni-0.35%Laの例として、No.23(熱処理温度150℃)、No.26(熱処理温度200℃)、No.29(熱処理温度250℃)
・Al-2.0%Ni-0.35%Laの例として、No.24(熱処理温度150℃)、No.27(熱処理温度200℃)、No.30(熱処理温度250℃)
本実施例は、上記実施例1の改変例であり、Al合金層として、Al-Ni-La-Cu合金層を用いた例である。詳細には、上記実施例1における表1に示す組成のAl-Ni-La合金層を用いる代わりに、表2に示す組成のAl-Ni-La-Cu合金層を用い、表2に示す熱処理を行なったこと以外は、実施例1と同様にして反射電極の各試料を作製した。次いで、上記実施例1と同様にして、接触抵抗値、Al酸化物層の最薄部の厚み、および酸素とAlの比([O]/[Al]比)を求めた。これらの結果を表2にまとめて示す。
本実施例は、上記実施例1の更なる改変例であり、Al合金層として、Al-(Ni/Co)-La-Ge合金層(Geは0原子%を含む)を用いた例である。本実施例では、特にGeの添加効果を示すためにAl合金の組成を設定しており、(Ni/Co)の含有量が0.2原子%と、本発明の範囲内(0.1~2原子%)ではあるが低めに設定した場合における、Geの添加効果(具体的には、接触抵抗値の更なる低減作用)を調べた。
本出願は、2007年12月26日出願の日本特許出願(特願2007-335003)、2008年12月19日出願の日本特許出願(特願2008-324373)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (15)
- 基板上に形成される表示デバイス用の反射電極であって、
前記反射電極は、
0.1~2原子%のNi及びCoのうち少なくとも一つ、並びに
0.1~2原子%のX(Xは、La,Mg,Cr,Mn,Ru,Rh,Pt,Pd,Ir,Ce,Pr,Gd,Tb,Dy,Nd,Ti,Zr,Nb,Mo,Hf,Ta,W,Y,Fe,Sm,Eu,Ho,Er,Tm,Yb,およびLuよりなる群から選択される少なくとも一種の元素である。)
を含有する第1のAl-(Ni/Co)-X合金層と;
AlとO(酸素)を含有する第2のAl酸化物層と、を有し、
前記第2のAl酸化物層が、透明画素電極と直接接続しており、
前記第2のAl酸化物層中のO原子数とAl原子数との比である[O]/[Al]が、0.30以下であり、
前記第2のAl酸化物層の最も薄い部分の厚みが、10nm以下であり、
前記反射電極が、前記第2のAl酸化物層と前記透明画素電極とが直接接続する領域において、前記透明画素電極と前記基板との間に形成されている反射電極。 - 前記第1のAl-(Ni/Co)-X合金層は、0.1~2原子%のNiを含有する請求項1に記載の反射電極。
- 前記第1のAl-(Ni/Co)-X合金層は、0.1~2原子%のNi及びCoのうち少なくとも一つと、0.1~2原子%のLa及びNdのうち少なくとも一つと、を含有する請求項1に記載の反射電極。
- 前記第1のAl-(Ni/Co)-X合金層は、0.1~2原子%のNiと、0.1~2原子%のLaと、を含有する請求項3に記載の反射電極。
- 前記第1のAl-(Ni/Co)-X合金層は、更に0.1~2原子%のZ(Zは、Ge、Cu、およびSiよりなる群から選択される少なくとも一種の元素である。)を含有する請求項1~4のいずれか1項に記載の反射電極。
- 前記第1のAl-(Ni/Co)-X合金層は、0.1~2原子%のNi及びCoのうち少なくとも一つと、0.1~2原子%のLa及びNdのうち少なくとも一つと、0.1~2原子%のGe及びCuのうち少なくとも一つと、を含有する請求項5に記載の反射電極。
- 前記透明画素電極が、酸化インジウム錫(ITO)および酸化インジウム亜鉛(IZO)のうち少なくとも一つである請求項1に記載の反射電極。
- 請求項1~4のいずれか1項に記載の反射電極を備える表示デバイス。
- 請求項5に記載の反射電極を備える表示デバイス。
- 請求項1~4のいずれか1項に記載の反射電極を備える表示デバイスの製造方法であって、
基板上に、スパッタ蒸着によってAl-(Ni/Co)-X合金層を形成する工程と、
形成したAl-(Ni/Co)-X合金層を、真空または不活性ガス雰囲気下で200℃以上の温度で熱処理する工程と、
スパッタ蒸着によって透明画素電極を形成する工程と、
を順次、包含する表示デバイスの製造方法。 - 請求項1~4のいずれか1項に記載の反射電極を備える表示デバイスの製造方法であって、
基板上に、スパッタ蒸着によってAl-(Ni/Co)-X合金層を形成する工程と、
形成したAl-(Ni/Co)-X合金層の上にスパッタ蒸着によって透明画素電極を形成する工程であって、前記スパッタ蒸着の少なくとも初期段階において、窒素成分を含有する蒸着雰囲気中でスパッタ蒸着を行う透明画素電極を形成する工程と、
を順次、包含する表示デバイスの製造方法。 - 請求項1~4のいずれか1項に記載の反射電極を備える表示デバイスの製造方法であって、
基板上に、スパッタ蒸着によってAl-(Ni/Co)-X合金層を形成する工程と、
形成したAl-(Ni/Co)-X合金層を逆スパッタする工程と、
スパッタ蒸着によって透明画素電極を形成する工程と、
を順次、包含する表示デバイスの製造方法。 - 前記Al-(Ni/Co)-X合金層は、更に0.1~2原子%のZ(Zは、Ge、Cu、およびSiよりなる群から選択される少なくとも一種の元素である。)を含有するものである請求項10に記載の表示デバイスの製造方法。
- 前記Al-(Ni/Co)-X合金層は、更に0.1~2原子%のZ(Zは、Ge、Cu、およびSiよりなる群から選択される少なくとも一種の元素である。)を含有するものである請求項11に記載の表示デバイスの製造方法。
- 前記Al-(Ni/Co)-X合金層は、更に0.1~2原子%のZ(Zは、Ge、Cu、およびSiよりなる群から選択される少なくとも一種の元素である。)を含有するものである請求項12に記載の表示デバイスの製造方法。
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- 2008-12-25 CN CN2008801226120A patent/CN101911157A/zh active Pending
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Also Published As
Publication number | Publication date |
---|---|
JP2009175719A (ja) | 2009-08-06 |
TW200934880A (en) | 2009-08-16 |
US20100231116A1 (en) | 2010-09-16 |
KR101230767B1 (ko) | 2013-02-06 |
US8384280B2 (en) | 2013-02-26 |
TWI390045B (zh) | 2013-03-21 |
JP4611417B2 (ja) | 2011-01-12 |
CN101911157A (zh) | 2010-12-08 |
KR20100080619A (ko) | 2010-07-09 |
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