TWI279860B - Method for forming metal wiring and method for manufacturing display device - Google Patents

Abstract

In the selected range of Cu wiring pattern (32) formed on the substrate (51), the electronegativity of the material of the wiring pattern (31) composed of TiN constructing the selected range is set to Xs. In the non-selected range of Cu wiring pattern, the electronegativity of the material of the insulation membrane (29) between layers composed of SiO2 constructing the non-selected range is set to Xn. The electronegativity of the organic metal material for forming the Cu wiring pattern (32) is set to Xm. The material satisfying the correlation formula of ""Xs < Xn < Xm"" is selected and the Cu wring pattern (32) is formed via the non-uniform reaction of the organic metal material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display device including a liquid crystal display device and a technique for forming an electric wiring used in ULSI or the like, and selectively forms copper or copper on a substrate. A method of forming the most appropriate metal wiring for the metal wiring of the alloy and a method of manufacturing the display device. BACKGROUND ART In recent years, in the field of semiconductors represented by LSI and ULSI, jade has discussed the possibility of using copper (Cu) as a wiring material to improve the progress of miniaturization by increasing the degree of integration of semiconductor devices. The speed of the action. In other words, compared with the wiring material used in the past, aluminum people can obtain low wiring resistance and high resistance to electromigration (1 &quot; stress ^(4) step (four) oil (10)), etc., in liquid crystal display devices, etc. In addition to the enlargement of the display area, it is possible to increase the degree of peripheral circuit and increase monolithicity in accordance with the increase in the display area. In addition, additional functions such as taxis, dynamic circuits and pixel built-in memory, etc., are widely used to check the driver and the like. Therefore, various types of display devices to be assembled in the future will increase the requirements for low-impedance wiring. In the same way as in the semiconductor field, as described above, the c° ratio of the wiring material is improved, and the wiring material A1 having superior low-resistance and resistance is developed to industrialize the active development. It can be seen that Cu 1279860 V. Invention Description (2) Although such a masking and reactive ion remanufacturing by ph〇t〇-lithography (reactiVe i〇I1 etching) It is difficult to form fine wiring with Cu to form a conventional fine wiring. In other words, the vapor pressure of cuogen is too low, and the self-synthesis of Cu is not easy to evaporate. Therefore, it is necessary to perform and remove the Cu-based compound formed by the above-mentioned engraving. The etching process is performed at a temperature of pr〇cess temperature UOO 〜30 0. That is, it is difficult to perform fine processing by the name of the wiring. In terms of the method of forming fine wiring by Cu, the special opening 1 in Japan 1 -1 3 5 5 0 4 discloses that this method is a so-called damascene method. First, an insulating film laminated on a substrate is formed on the insulating film laminated on the substrate to form a desired wiring pattern in advance. In order to be inserted into the groove, the Cu film is entirely transmitted to the inside of the groove and the insulating film. In this case, PVD (Physical Vapor Depositon) such as sputtering is used to insert Cu into the groove. And various methods such as a gold plating method or a CVD method using an organic metal material. Thereafter, the surface of the substrate is removed by a film until it is embedded in the upper end surface of the groove portion. The method includes a polishing method such as chemical mechanical polishing (CMp: Chemicai Mechanical Polishing), etch-back, etc. By the above step, the Cu film remains only inside the groove, thereby forming an embedded type. Cu wiring pattern. Other methods can be used to arrange the catalyst such as Pd on the substrate to the desired wiring pattern.

Page 6 1279860 V. Description of invention (3) (Η - Nimo, . Yabe, Appl. Phys. Lett., 63, 3527-3529 (1993)) - ^ The method is based on the formation of a pattern of Pd, etc. (4) In addition, it is also possible to form a wiring pattern of Cu in the electroless ore I. In addition, it is also possible to form a conductive pattern by using a conductive material as an electrode on an insulating substrate. Methods. OBJECTS TO BE SOLVED BY THE INVENTION Although the above-described conventional methods for forming Cu in the past have been made, there are the following problems. The ice blade 百 百 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。瓜八去' has the first and the intrusion method, in order to form a wiring pattern that connects the trenches, it is necessary to pass through the vias (via) to form the film-forming project, the lithography round plan, and the manufacturing process of the upper and lower engraving projects. It is very complicated. Wang’鍅 Second, in order to reduce the wiring resistance, it is necessary to increase the wiring film thickness. However, when a high aspect ratio (aspect rati) is used, the acceptance of Cu is deteriorated. w layer hole (via third, the Cu film is formed on the substrate after the film is formed on the substrate for the above-mentioned CMP project, etc., there is a problem that the throughput of the process is poor (through-put). In order to produce a LSI or ULSI diameter of 12 吋 (; [the size of the wafer, a large CMp device has been developed in the past.), the substrate size for manufacturing the liquid crystal display device is large. Large-scale substrate, compared with the use of LSI, etc., because = 丨 丨 · 5m positive, A Ji quasi flat page 7 1279860

V. INSTRUCTIONS (4) Large areas of the nature require grinding work. That is to say, it is difficult to put the embedding method on the display device side. In the case of a liquid crystal display device using a large substrate, it is assumed that the above-described CMP method can be removed by the overall polishing and etching methods, and there is a problem that the price of the q is too high. That is to say, the portion of the Cu film as the @@ line on the liquid crystal display device is extremely small compared with the area of the glass substrate. Therefore, it is necessary to remove most of the film-formed Cu film. As a result, high-priced Cu materials are used, and the efficiency of use is very poor. In addition, there are the following problems in selecting a film formation method using gold plating.

First, the use of mineral gold for film formation has a practical effect on a large printed circuit board. However, in the case where LSI, ULSI, or a display device or the like is required to form a wiring pattern, the composition of the gold plating liquid may change over time, which causes instability in the manufacturing process. There is a problem that impurities may infiltrate to cause deterioration of the film quality, and the liquid medicine may also affect the environment. Second, after the basic wiring is formed, the method of extracting the Cu thin film on the conductive portion by using gold plating has superior selectivity. However, it is necessary to coat the reverse side, the unnecessary part of the conductive surface, and the work for forming the energized basic conductive pattern. This causes problems of complicated process and high cost. Third, a large amount of impurities are infiltrated into the Cu thin film formed by the gold plating method, and the electrical resistance of the formed Cu thin film tends to be high. That is to say, in the gold plating method, it is necessary to have an annealing after film formation. Due to the annealing treatment, the gold plating method is difficult to apply to a large-area display device or the like from the viewpoint of heat resistance of the substrate and the like.

1279860 V. INSTRUCTIONS (5) - The same as the wafer substrate on which Ls 1 was fabricated in the past, the size of the substrate used to make the device is as described above. In view of this, in order to uniformly process the gold plating treatment 2 of such a large substrate. Because it requires a large amount of medicines, it will cause adverse effects on the environment. It is not suitable for the above-mentioned problems. Recently, I tried to make ^

The Cu-CVD method was selected to form (9) a film. The following method is disclosed in, for example, Japanese Patent Publication No. 6-236879. First, on the base metal film of the wiring shape, metal particles composed of a Vm group metal which extracts Pd or the like and which is expected to have a hydrogen dissociation ability are selected. In this case, a carrier gas having two hydrogen atoms is introduced into the organic metal material Cu, and a film is formed by thermal decomposition. By this method, on the v j丨 group gold having a high hydrogen dissociation ability, the hydrogen of the carrier gas introduced simultaneously with the organometallic material Cu is dissociated. As a result, the organometallic material Cu is preferentially reduced on the VI 11 metal. Therefore, a Cu core can be formed on the V111 group metal and a film growth can be selectively performed. Therefore, a Cu thin film can be selectively formed on the substrate. However, in this method 'because the reduction reaction is carried out on the V 111 group metal on the surface of the substrate', it is necessary to use hydrogen as a carrier gas. At this time, the reduction reaction of the organometallic material can also be carried out by hydrogen gas present in the gas phase. Therefore, by the reaction of the reactants produced in the gas phase, even on the surface outside the selected range, a core of Cu is formed. This has the problem of deteriorating the selectivity of Cu film formation. In addition, because the engineering of the V111 group metal must be selectively extracted on the base metal, the process is increased. Moreover, since hydrogen is required in the process, in order to ensure the safety of the process, the cost of the safety equipment and the like after the film formation process is also a problem. 1279860

5-949 another 7. In addition, as for the method of forming a film by I, the technique of the following is disclosed in R. Using a first material of a large electronegativity or a second material of: M, 〇F 5 ί to be mixed on a surface of a semiconductor substrate to produce 6 疋 06, a metal halide or a commercialization of the metal: original, and a mixed gas of reducing gases of h2, C0, and SlH4. When the mixed m electric field is applied to the semiconductor substrate, the discharge of the material gas = stack L. The metallographic phase on the second material (IV) Selectivity and direction It is described that by this technique, a metal film which selectively forms a film can be obtained due to the relationship between the material gas and the material constituting the surface of the substrate. However, by using the plasma by decomposing the discharge of the material gas, even in the gas phase, the metal core (366(1) of the decomposition product of the material gas can be formed, which is easily deposited non-selectively on the substrate. There is a problem that it is easy to hinder the selective deposition of the metal film. Further, by forming a film using a reducing gas, the reverse side of the film forming speed can be raised, and the decomposition of the material gas can be carried out by the reaction in the gas phase. Therefore, it is also easy to hinder the selectivity of film formation.

In addition, in this technique, it is necessary to use a reducing gas having a igniting and igniting H2 and Si. Therefore, the cost of safety equipment to ensure the safety of the process is also reflected in the total process cost. It is also known that W and Μ 〇 have higher resistivities than C u and A 1 (w : 5 6 X1 Ο -6 Ω cm (300K), Μο: 5·2 χ 10_6 Ω 〇ιη (0. C), Cu: l7xl 〇 _ 6Qcm (20. C), Al: 2.6xl0-6Qcm (20 ° C)). A film formed of such a large resistivity w and M 通常 can also be suitably applied to an LSI and an IC which are connected between the laminate layers in the up and down direction.

Page 10 1279860 V. Description of invention (7) Wiring. However, the broadcast-, and/or I a of the display device represented by w and Mo are used as the liquid crystal display device 卽i ^ π 1 to describe the wiring and signal wiring. The higher the resistivity of the wiring, the wiring of the slave, and the wiring of the scanning wiring and the signal are used as the scanning wiring 2m. To this end, it is harmonious. Switched. When q breaks the wiring, it is impossible to operate a good σ. Second = surgery; gas decompression to 5 - dragging the invention I ", and then introducing into the vacuum container is inconvenient. The present invention has the above problems 'not and can provide - metal wiring body, method, selected to form a low impedance The wiring method of the invention is a method for forming a metal wiring in which a metal wiring is selected, and a material constituting the selected range. The electronegativity is set to Xs, at least in the vicinity of the selection range, the non-selection range of the aforementioned metal wiring is not formed, and the electronegativity of the material constituting the non-selection range is set to Xn, and the organic metal material for the metal wiring of the shape 1 is formed. When the electronegativity is set to Xm, the relationship between each electric negative 曰α XS&lt;Xn&lt;Xin is (Xm-Xn)&lt;(Xm_Xs). By selecting materials with full relationship This can be achieved. (Application No. Scope) This electronegativity is a property value indicating the supplyability of electrons, and the ability of an atom to attract electrons when chemically coupled. That is, the electrical quantity of the material in the present invention. Is indicating that the material is for The electron property value, the ability of the material to generate a chemical reaction, and the ability to attract electrons. In the present invention, the electronegativity of each material can also be constructed. Page 11 1279860 V. Invention Description (8) ^^__ The electronegativity is calculated on average. Therefore, between two different electrical negative degrees, a material with a small electronegativity is established for the material with a large electronegativity from the relationship between the buds. In order to form a thin film of organic gold (organic Cu material) into the surface of the substrate. 'Organic metal material is dissociated and adsorbed from the surface of the substrate by charge exchange between the surfaces of the substrate. Therefore, it is adsorbed from the surface of the substrate. The two organometallic molecules (organic Cu molecules) in the feed are moved from the surface of the substrate, thereby causing oxidation between the two organometallic molecules, that is, a so-called heterogeneous reaction. Therefore, the organic metal material is extracted. Metal (Cu). By this reaction, the accumulation of metal film can be known (JAT Norman 5 et. al., Thin Solid Films, Vol. 262 (1 995) PP46-51). 'Inhomogeneous reaction (again It is a result of a reduction reaction in which two or more molecules are oxidized by two or more molecules, and two or more kinds of substances are produced. Here are two organometallic molecules (the above examples are Between the jCu molecules, oxidation is carried out as described later, and a reduction reaction is carried out to produce a reduced metal atom and an oxidized organometallic compound, and finally a film formation of a metal thin film is performed. / Thus, the organic metal material is introduced by the present invention. When the range of the surrounding and non-selected ranges is included, 'the exchange of electrons between the surface of the selection range of the difference in the direct-size relationship and the organometallic material due to the aforementioned relationship of the electronegativity. In general, organometallic materials attract electrons from the surface of the chosen range. In other words, by electronic exchange, the selection range can be prioritized and selected.

Page 12 1279860 V. INSTRUCTIONS (9) Dissociation and adsorption of organic metal materials. (Application No. 1 of the patent application) The method of forming a metal wiring according to the invention may form a metal wiring by a chemical reaction of an organic metal material. (Patent No. 2 of the patent application) = The method for forming the metal wiring of the invention, as described above, in order to allow the organic gold, Ϊ to select a range of preferential adsorption, to form a film unevenness reaction: a large number of organic metals molecule. In other words, the choice range is excellent. Therefore, the formation of the nucleus and the film deposition can be performed in the selection range. From the surface of the 2m range, due to the above relationship, the organometallic ruthenium will be organically ΐίί. Therefore, when compared with the surface of the selected range, it is not allowed to attach to the surface of the non-selected range. That is to say, there are few organometallic molecules for the heterogeneous reaction of the film 4, and it is not easy to accumulate the results on the surface of the selected range and the surface of the non-selected range. A so-called incubation period occurs. Due to this latency: the difference between the films, the selectivity of the film. Therefore, it is possible to improve Cu, etc. That is to say, the choice of the range of the selection, the non-selection 2 of the electronegativity is to satisfy the above relationship = the heterogeneous reaction of the surrounding material, and the formation of the metal wiring shake machine: Stacked up. In other words, you can: Select the line. (Applicant's scope of the second item)

The method of forming the entire wiring may be a metal wiring by a chemical vapor deposition method (10) method of forming a metal-bonded metal film. (申J

Page 13 1279860 V. Invention Description (10) Patent Area No. 3) By using the above different Rays: adsorption difference, it is possible to selectively form a metal wire. Otherwise, the metal material is difficult to etch. It is possible to obtain a wiring having low resistance and excellent composition without using a composition. (Patent No. 3 of the patent application), and a transferable Cu, etc. The composition of the metal wiring of the present invention is selected from the group consisting of φ.Ti. (Applicant's 4th item) is not a r-battery material, or ‘. 3 and so on oxide = with f = into. Γ由## &lt;, ^ u Insulation material for milk is taken (Shenqi patent scope No. 5, 6) The choice of the surface of the leaf juice is made up of organic materials in the selected range of conductive materials. The surface of the organic metal; the external surface of the non-selective insulating material, in order to form a metal with a factor: ί = sheet metal: the adsorption ratio of the molecule is less than the selected range, and the organic surface mobile charge is difficult. Therefore, it is difficult to make the upper and the non-uniform reverse: etc., that is, it is said that it is difficult to adsorb the organic metal, and the difference between the formation of the film in the ^ and the non-selected circle is 0. ° Therefore, metal wiring can be formed in a state of high selectivity. (Application No. 4, 5, and 6) The method for manufacturing a display device according to the present invention includes a matrix-shaped design complex drawing, page 14 1279860, a pixel electrode of the invention (11), and a plurality of pixel electrodes. A plurality of connected thin film transistors, and a plurality of scan wirings and signal wirings for driving the thin film transistors. The selection range of the wiring of at least one of the scanning wiring and the signal wiring is formed, and the electronegativity of the material constituting the selection range is Xs. The non-selection range of the aforementioned wiring is not formed and the electronegativity of the material constituting the non-selection range is set to Xn. The electronegativity of the organometallic material for forming the wiring is set to Xm, and each electronegativity is a relationship of Xs &lt; xn &lt; Xm, i.e., (Xm - Xn) &lt; (Xm - Xs). This can be achieved by selecting materials that satisfy these relationships. (Applied No. 7) τ〜犯圆 In addition, the present invention is applied to a method of manufacturing a display device in which a thin film transistor and a pixel electrode are connected by electric wiring, and an electric wiring is formed and the material constituting the selected range is electrically The negative is set to Xs. The X-ray selection range is not set and the electronegativity of the material constituting the non-selection range is set to 'electrical parameter; the electronegativity of the organic metal material of the γ-forming electrical wiring is set to Xm, ίi t :&lt;xnfm That is, the relationship of (xm-xn) "xm-xs". By choosing metal materials, I can spring! Buried 2 is achieved by dissociating the 有机μ of the adsorbed organic wiring, forming the scanning wiring, the signal wiring, and the electrical wiring ^ (4). (In the case of (4), the other organometallic material is Cu or the county white Γ &amp; person a ” material, and it can also be obtained by the organic gold ^ 2 u, s, the organic metal wire m2 属 genus And the wiring of the scan distribution area (g) is formed. (Applicable to the c-line, signal wiring, and wiring of the electric wiring ty and the Tetsuji-ji Temple.)

Page 15 1279860 V. INSTRUCTION OF THE INVENTION (12) The following is abbreviated to the following. Embodiment 1 Hereinafter, the film is used as a film for buf fering. The insulating film of the crystal si or the like is then formed on the surface of the A1 group by the solid film of the A 1 film of the film of 10 nm. Further, the surface electronegativity at the constituent element is 2.93. Next, the introduction is as shown in A1. For the detailed description, please refer to the related drawings of the embodiment of the present invention. In the description of the drawings, the same functions are denoted by the same symbol, and the description. According to a first embodiment of the present invention, a method of forming a metal wiring composed of Cu in a glass or the like is described. On the non-inspective glass substrate of the liquid aa display device, the thin layer of cerium oxide (SiO 2 ) film is formed as a substrate for I50 nm by plasma CVD, and the other may be used in the single crystal stone ( On the substrate composed of a single 1 icon), a thermal oxide film (si 〇 2 film) is placed on a germanium substrate, and the aluminum (A1) film is formed by sputtering. The lithography and etching are then performed. In the engineering, the wiring pattern of the predetermined shape is processed. By this work, the surface of the selected range of the substrate and the non-selected range of the composition of the Si 〇 2 film are the definitions of the average of the electronegativity of the material of the two or more elements of the present embodiment. That is to say, the selection range of the composition of A1 is 1.25, and the insulating substrate 2 formed by the wiring pattern of the electron-negative composition of the material composed of two or more elements of S i 02 is as shown in FIG. Reaction chamber of CVD device

Page 16 1279860 DESCRIPTION OF THE INVENTION (13) Inner 0 Here, the CVD apparatus shown in Fig. 1 will be described. The substrate 2' for forming a Cu film is disposed on a stage 3 in the reaction chamber 1 of the vacuum vessel as shown in Fig. 1. Reaction room! The vacuum exhaust system (not shown) is used to exhaust the turbine tool (turb〇 - m〇iecuiar - pump) until it reaches the vacuum level. Then, the substrate 2 in the reaction chamber 1 is introduced, and is heated to a predetermined reaction temperature by a heater (not shown) provided in the two units 3. The substrate heating at this time is not limited to the heater, and a lamp annealing may be used. The organometallic material 5 composed of a liquid Cu organometallic compound by nitrogen gas 10 is extruded from a raw material tank (1 «Heart 1 &amp; 1^]: 413 178111^4. The introduction amount of the organometallic material is controlled by a liquid flow meter. Control 6. The organic metal material 5 is then heated by the gasifier 7 to increase the vapor pressure of the organometallic material 5. Thus, the organometallic material 5 becomes an organometallic gas composed of vaporized organometallic molecules. The gas and the nitrogen gas 10 of the carrier gas are introduced into the reaction chamber 1 through the gas introduction portion 8. Further, 9 is a gas discharge portion. For the organometallic material 5 of Cu, for example, a monovalent complex of Cu (Cu (hfac) TMVS: hfac = Hexafluoroacetylacetonate (CF3COCH COCF3), TMVS = Trimethylvinylsilane (C05H12Si), etc. Fig. 2 is a schematic view showing decomposition and deposition reaction of Cu organometallic material 5. Fig. 1 is introduced into the reaction chamber 1 An organic metal material (hereinafter referred to as an organic copper material) 5 is in contact with the substrate 2 disposed in the reaction chamber 1 and is dissociated and adsorbed on the surface of the substrate 2. Therefore, the organic copper material 5 is heated by the heated substrate.

1279860 V. Inventive Note (14) (thermal energy), forming a "film" by the following reaction. Step 1: In the gas phase (g), by decomposing and desorbing TMVS in the organic copper molecule, forming a monovalent The intermediate product of copper oxide atoms (Cu(hfac)(g)) is adsorbed by the surface of the substrate 2 (a). 2Cu+1(hfac)(a)-&gt;2Cu+1(hfac)(g) + TMVS (g) f 2Cu+1 (hfac) (a) Step 2 · The two organic copper molecules on the surface of the adsorption substrate 2 are in contact with each other on the surface of the substrate 2. Therefore, the two organic copper molecules are used for unevenness. In the reaction, a reduced copper molecule Cu(s) is extracted and deposited to form a Cu thin film, and a reaction product which is oxidized to divalent is formed to be removed from the surface of the substrate 2 by a gas phase. 2Cu+1( Hfac)(a)—Cu(〇)(s)+Cu+2(hfac)2(g) The electronegativity of an organic copper molecule Cu(hfac) adsorbed on the surface of the substrate 2 by the above reaction is as before Similarly, the arithmetic mean of the constituent elements is 3.4. Therefore, the selection range M of the surface constituting the substrate 2 is based on the electronegativity relationship of SiO 2 in a non-selected range.

Al&lt;Si02&lt;Cu(hfac) = 1.5&lt;2.93&lt;3.24 Therefore, between the selection range A1 and the organic copper molecules, electrons are supplied from the surface of A1 in accordance with the electronegativity relationship. Therefore, the efficiency of attaching the organic copper molecule Cu(hfac) to the US handle, is enhanced. ' Surface and 1279860 V. Description of invention (15) Table 1 shows the electronegativity of the element. Element name Electronegativity Element name Electronegativity Μ 1.5 Μ) 1.8 12 Ta 1.5 Si 1.8 W 1.7 Q 1.6 〇 3.5 Μ 1.8 N 3.0 Cu 1.9 F 4.0 Τι 1.5 C 2.5

In the first embodiment, the organic copper gas is obtained by heating Cu (hfac TMVS of the above-mentioned organic copper material 5 to about 40 ° C, increasing the vapor pressure gas of the Cu (hfac) TMVS, and then using nitrogen gas W as a carrier gas'. (The gasified organic copper pattern is not introduced into the reaction chamber 1. At this time, the inner wall of the chamber 1 through the organic copper gas is prevented from being inhibited by the adsorption and adsorption of the organic copper gas, and is maintained at about 40~ The temperature of 60 ° C. The film forming conditions are organic copper; i _ gas flow 28 〇 SCCM reverse = ^ plant supply flow, carrier gas nitrogen

The temperature m of the substrate 2, the pressure 13 core (1^), and the wiring pattern formed by the enthalpy of the reaction chamber 1 were deposited on the film for 8 minutes. As a result, the film 2 on the substrate 2 is oxidized, and the film is formed into a film having a film thickness of 16 〇 n_Cu. In addition, it was confirmed that no &lt;film, (leak) was deposited on the surface of Cu with t j . - separate electrical leakage between the line patterns

Page 19 1279860 V. Inventive Note (16) Further, in the first embodiment, although the temperature of the substrate 2 in the reaction chamber 1 is set to 160 ° C, it is most preferable to set the temperature of the substrate 2 in the reaction chamber 1 Set to 120. C~190. C. When the temperature is lower than 120 ° C, it is necessary to increase the activation energy (act i vat i on energy) necessary for the film formation reaction described above, otherwise a good reaction cannot be performed. On the other hand, when it exceeds 190 ° C, the activation energy necessary for the film formation reaction described above becomes low, and the above reaction is produced not only in the range of selection but also in the non-selection range, so that the selectivity is lowered. Thus, the electronegativity Xs of the selection range (A1) of the Cu wiring pattern 32 formed on the substrate 51 is 1.25, and the electronegativity χη of the non-selected range (Si〇2) of the Cu wiring pattern (32) is not formed. It is about 2.93, and the electronegativity Xm of the organic copper material 5 for forming the Cu wiring pattern (32) is 3.4. Therefore, as long as a material satisfying the relationship of xs &lt; Xn &lt; xm is selected, the Cu wiring pattern (32) can be formed by the heterogeneous reaction of the organometallic material. EMBODIMENT 2 In the second embodiment of the present invention, a display device including a thin film transistor 55 is a preferred example of forming a metal wiring by a Cu thin film, and an element side of an active matrix type liquid crystal display device 50 is exemplified. Fabrication of substrate 51. FIG. 3 and FIG. 4 show a liquid crystal display device 5〇. Further, it is indicated by omitting the auxiliary capacity in Fig. 3 and Fig. 4. As shown in FIG. 3 and FIG. 4, the liquid crystal display device 5A includes a pair of front and rear transparent substrates 51 and 52, a liquid crystal layer (not shown), a halogen electrode, and a thin film transistor (TFT: Thin Film TranSist). 55, scan wiring 5 /, signal 曰酉曰

1279860 V. DESCRIPTION OF INVENTION (17) Line 57, scanning wiring terminal 58, signal i line terminal 59, counter electrode (four), and the like. The front-rear-pair transparent substrate 51'52 can utilize, for example, a pair of glass substrates. Hereinafter, the transparent substrates 51, 52 are referred to as glass substrates. These glass substrates 51 and 52 are joined by a sealing material (s e a ) which is not shown in a frame shape. - the liquid crystal layer is disposed on a pair of glass substrates 51, 52 surrounded by a sealing material as shown in FIG. 4, a pair of glass substrates 51, from one of the glass substrates 51, such as in the latter The inner surface of the side glass substrate (element side substrate) 5 i is provided with a transparent complex pixel electrode 54, a plurality of thin film transistors 55 'scanning, wiring 57, a plurality of scanning wiring terminals 58, and a plurality of signal wiring terminals. The pixel electrodes 54 are designed in a matrix in the row and column direction. 5 and each of the plurality of halogen electrodes 54 are electrically connected. Scan wiring 56/ and? The two 57 and the thin film transistor are electrically connected. A plurality of scanning wiring terminals "and a plurality of wiring terminals 59 are formed at one end edge portion and one side edge portion of the substrate 51, and f scanning wirings 56 are formed along each row of the pixel electrodes 54. These scannings are provided. One end of the wiring = is connected to a plurality of scanning wiring terminals 58 provided at one side edge &amp; of the rear substrate 51. The plurality of scanning wiring terminals 58 are each connected to the signal driving circuit 60. ' 〇 Additional # wiring 5 7 Each of the signal wirings 57 is connected to a signal wiring terminal 59 provided at one end edge of the rear substrate 51. The plurality of signal wiring terminals 59 are connected to each other. The image signal circuit 61. The inner surface 1279860 of the glass substrate (opposing substrate) 52 on the front side of the other glass substrate. 5. The invention (18) is provided with a film-like transparency opposite to the plurality of pixel electrodes 54. The counter electrode 6 2 may have a plurality of pixel portions on the inner surface of the glass substrate 52 on the front side, a plurality of pixel electrodes 54 and the counter electrode 62 facing each other, and color filters corresponding to the plurality of pixel portions. Light Further, a light shielding film may be provided on the inner surface of the glass substrate 5 2 on the front side so as to correspond to the range between the above-described halogen portions. A polarizing plate (not shown) is provided outside the pair of glass substrates 51 and 52. Further, in the transmissive liquid crystal display device 5, a surface light source (not shown) is placed on the rear side 0 of the rear glass substrate 51. Further, the liquid crystal display device may be reflective or semi-transmissive. Fig. 4 is a cross-sectional view showing the vicinity of a thin film transistor 55 of the liquid crystal display device of the second embodiment. 2 2 is a buffer layer composed of S i 02, and 23 is a polycrystalline silicon (Poly - Si: p 〇lysiiicon) film, 26 is the source range, 27 is the drain range, 28 is the channel range, 24 is the gate insulating film composed of Si 02, 25 is the gate electrode composed of A1, and 29 is the interlayer insulating film composed of SiO 2 40 is a source line 26 of the thin film transistor 55 and an electric wiring connected to the halogen electrode 54, 31 is a wiring pattern of TiN composition, and 32 is a Cu wiring pattern. The manufacturing process of the thin film transistor of the second embodiment will be described below. The thin film transistor of the second embodiment is as shown in FIG. 5(a)~ e) The engineering shown is shown. First, as shown in Fig. 5 (a), a monohydrate (S i 〇 2 ) film is formed on the glass substrate 51 of the insulating substrate as the buffer layer 2 2 . The film thickness of 2 is, for example, a film thickness of 150 nm. On the buffer layer 22, an amorphous germanium (a-Si) film having a film thickness of 8 nm is formed by a reduced pressure CVD method at a substrate temperature of 430 ° C. Forming

Page 22 1279860

The a-S_i film utilizes laser annealing of excimer laser light (丨"" anneaung), a... Thus, a polycrystalline germanium (p〇ly-Si) film was formed. In order to obtain the crystallization process of the crystallization film, t can also be obtained by about _. Thermal annealing of C is carried out by solid phase growth engineering. Next, with respect to the obtained polycrystalline germanium film, the photoresist of the photosensitive resin was applied by a spin coating method. Therefore, the exposure and development of the photoresist film (resist-fUm) is performed by lithography, so that a predetermined island shape is formed. By dry etching using CF4 gas (dry etching method), an island-shaped polycrystalline germanium film 23 as shown in Fig. 5 (a) is formed. Next, the glass substrate 51 including the island-shaped polycrystalline germanium film 23 is comprehensive. The gate insulating film 24 composed of a 31 〇 2 film is formed to have a film thickness of 1 〇〇 11111. This film formation is performed by using a TEVS (Tetraethyl Orthosilicate) as a raw material by a plasma cvd method. Further, the gate insulating film 2 is not provided. Patterning of 4 (not shown). Next, in order to form a gate electrode, a film is formed by a sputtering method. The A1 film is processed by a lithography method and an etching method to form a film as shown in Fig. 5 (1). The gate electrode 25 is shown. This gate electrode 25 is used as a mask, and the polysilicon film 23 is doped with impurities such as phosphorus (P) 33. By using this gate electrode carrier as The mask is implanted into the polysilicon film 2 3 other than the lower portion of the gate electrode 25. The self-integrating source region 26 and the drain region 27 are formed, and after the impurity is implanted, activation is performed. Processing. Thus, the source and drain ranges 26, 2? which are not introduced as shown in Fig. 5) are formed. 28 through quality. Next, a Si 2 film having a thickness of 300 nm was deposited by a plasma CVD method to form an interlayer insulating film 29 as shown in Fig. 5 (c). Continue to use lithography and

V. INSTRUCTION OF THE INVENTION (20) The source and drain ranges 26, 27 and the gate insulating film 24 are removed by an etching method. In this way, the contact hole 29 of the source and drain regions 26, 27 is formed by the contact hole (the level of the contact hole 30 and the upper layer of the interlayer insulating film 29) 30 shown by c〇nU C . This is followed by a titanium (TiN) film. Therefore, the nitriding film portion of f20 〇 nm is covered by the lithography method to form a photoresist film. Then, the wiring pattern 31 composed of the ruthenium and the desired Τ Ν film is used. Figure 5 (d) does not use the Cu-cvd shoe as shown in Figure 1. The substrate 2i of the thin-film transistor 5 5 is subjected to the selection of c: (d). The hole 30 is shown. And the yttrium film formed on the periphery thereof constitutes the electronegativity 疋2.5 of the pattern 31. In addition, the interlayer insulating machine composed of the Si〇2 film is made of copper (5:}11^(:) ^^^8 Degree relationship is,

TiN&lt;Si02&lt;Cu(hfac) = 2. 5&lt;2. 93&lt;3.24 The organic copper molecules on the introduction substrate 21 are preferentially adsorbed on the wiring pattern 31, so the organic copper molecules introduced onto the substrate 21 are not as described above. The homogenization reaction starts the decomposition reaction. Thus, the Cu wiring pattern 32 selected on the wiring pattern 31 as shown in FIG. 5 is formed. The film formation conditions were a supply flow rate of the organic copper material 5 of 〇〇·8 g/min, a carrier gas flow rate of 5^SCCM, a film formation pressure of 266 Pa (2T〇rr), and a substrate temperature of 17 Å. c, enter the film for 15 minutes. At this time, a (3) wiring pattern having a film thickness of about 2 〇〇 ηηη was formed, and a Cu film deposited on the interlayer insulating film 29 was not observed, and leakage between the Cu wiring patterns 32 was not confirmed.

As described above, the electronegativity Xs of the material of the wiring pattern 31 of the TiN composition of the selected range is selected to be 2.5 in the selection range of the Cu wiring pattern 32 on the substrate 51. The electronegativity of the non-selected range of the Cu wiring pattern 32 is not formed, and the electronegativity X^n of the organic copper material 5 for forming the Cu wiring pattern 32 is 3·24. . Therefore, as long as a material satisfying the relationship of xs &lt; Xn &lt; Xm is selected, the wiring pattern 32 can be formed by the uneven reaction of the organic metal material. In other words, by the method of the second embodiment, the signal wiring 57 and the electric wiring 4 connected to the thin film transistor and the pixel electrode 54 can be selected on one surface of the element side substrate 51. Further, in the second embodiment, as in the first embodiment, the wiring wiring 57 and the thin film transistor 55 and the halogen electrode 54 are connected by the Cu thin film, and the scanning wiring 56 can also be selected by the Cu thin film. form. As described above, the method of forming the metal wiring according to the first and second embodiments is characterized in that the method of forming the metal wiring is selectively formed in the selected range, and the electronegativity of the material having the f selected range is "at least" In the vicinity of the aforementioned selection range, the non-selection range of the metal wiring is not formed, and the electronegativity of the material constituting the non-selection range is set to χη, and the electronegativity of the organic metal material for forming the metal wiring is set to Xm, each electronegativity is a relationship of X^&lt;, Xn&lt;Xm. (Patent application item i) is additionally characterized by forming the aforementioned metal wiring by calling the heterogeneous reaction of the organometallic material (application Patent Model (No. 2) is additionally characterized in that the aforementioned metal wiring is formed by using the chemical emulsion phase growth method of the above-described organometallic material and the Cu thin film. (Patent Patent No. 3), that is, by selecting these materials, So that the relationship of Xs&lt;Xn&lt;Xm is satisfied,

Page 25 1279860 V. INSTRUCTIONS (22) It is possible to preferentially adsorb organic metal materials of film-forming species. In addition to the selective adsorption of organometallic materials, the organometallic materials can be preferentially selected in the selected range. The uneven response. (Patent No. 2 of the patent application) In addition, a selective film formation method of a Cu film can be realized by a chemical vapor deposition method with good selectivity. (Patent Application) Further, by forming a metal wiring by using a chemical vapor phase growth method (CVD method), it is possible to selectively form a film by utilizing the difference in the adsorption electron metal material by the above different electronegativity. Further, it is possible to obtain a wiring such as Cu having low resistance and excellent migration resistance without using a difficult etching method. (Patent No. 3 in the patent application scope) In other words, in the method of forming the metal wiring according to the first and second embodiments, a reducing gas such as hydrogen or the like can be used, and by the heterogeneous reaction of the organic metal material, The gold wire 0 formed by forming the Cu film selected on the glass substrate is further characterized in that the material constituting the above selection range contains at least A ^,

A conductive material of one of Ti, Ta, W, and Si. The material that constitutes the non-selection range (application for patent 4) is an insulating material composed of oxides or nitrides such as Μ% or η〇. (Applicant Patent Sections 5 and 6) In this way, the migration of the organometallic material on the surface of the selected range can be utilized: the unevenness reaction can be promoted. That is to say, a method of forming a metal wiring composed of a Cu thin film with high selectivity can be provided. In addition, it is possible to obtain a wiring composed of Cu having low impedance and excellent migration resistance without using an etching method. That is, a semiconductor element typified by lsi and ULSI and a display represented by a liquid crystal display device

Page 26 1279860 V. INSTRUCTIONS (23) Device A wiring that can provide Cu with superior characteristics. Further, since the CU wiring can be formed only in the necessary portion, the utilization efficiency of the film-forming material Cu necessary for film formation can be improved. Therefore, it is possible to reduce the material cost and simplify the engineering, and provide a method of forming the Cu wiring. According to the second embodiment, the method for forming a display device includes a plurality of matrix-shaped halogen electrodes, a plurality of thin film transistors each connected to the pixel electrode of the complex f, a plurality of scanning wirings, and signal wiring for driving The thin film transistor is characterized in that a selection range of wirings for forming at least one of the scan wiring and the signal wiring is formed, and an electronegativity of the material constituting the selection range is set to Xs, and non-selection of the wiring is not formed. The range is such that the electronegativity of the material constituting the non-selection range is Χη, and the electronegativity of the organometallic material for forming the above-mentioned = line is Xm, and each electronegativity is a relationship of Xs &lt; Xn &lt; Xm. (Patent No. 7 of the patent application) Further characterized in that the thin film transistor and the pixel electrode are electrically connected, and the selection range of the electric wiring is formed and the electronegativity of the material constituting the selection is set to Xs, the non-selection of the above-mentioned electric wiring is not formed, and the electronegativity of the material in the non-selected range is set to Xn, and the electronegativity of the organic metal material forming the electric wiring is set to Xm. The respective electronegativity is the relationship of Xs &lt; Xn &lt; Xm. (Application No. 8 of the patent application) It is said that it is possible to form an organic metal material which adsorbs a film-forming species with priority in selecting a scanning wiring, a signal wiring, and an electric wiring-self-selection range. The above-mentioned organometallic material is an alloy of CU or a ruthenium, and at least one of a known wiring, a signal wiring, and an electric wiring is formed by the uneven reaction of the organic metal material.

1279860

Wiring. (Application No. 9 of the patent application) In this way, a reducing gas having a low resistance and a good migration resistance can be selected without using a reducing gas such as hydrogen or the like. Even if the embedding method and the splash method are not necessary, it is not necessary to simplify the film formation of the Cu film on the substrate, and it is not necessary. In other words, it is possible to manufacture a display device having scan wiring and signal wiring having low and non-migration resistance. Further, the Cu film can be formed at a film formation pressure of 1T 〇rr to 2T rr, that is, the cost of the pressure reducing device or the like is reduced as compared with the technique disclosed in Japanese Laid-Open Patent Publication No. Hei 5-94970. Simple and inexpensive manufacturing of display devices'. According to the present invention, it is not necessary to use a reducing gas such as hydrogen, and a method of forming a metal wiring can be provided, and a wiring having low resistance and good migration resistance can be selected. Further, the embodiments of the present invention have been specifically described. However, the present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the scope of the invention. Industrial Applicability The metal wiring of the present invention can be used for a metal wiring including a semiconductor device represented by LSI and ULSI and a display device represented by a liquid crystal display device. The method of manufacturing a display device of the present invention can be utilized for the production using a liquid crystal display device and an organic EL or an inorganic EL.

Page 28 1279860 Brief Description of the Drawings The first drawing is a schematic configuration diagram of a Cu chemical vapor deposition apparatus referred to in the first embodiment of the present invention. The second drawing is a schematic view of the deposition reaction by the Cu organometallic material in the present invention. The third drawing is a plan view of a part of the liquid crystal display device mentioned in the second embodiment of the present invention. The fourth drawing is a cross-sectional view of the vicinity of the thin film transistor of the liquid crystal display device of the third drawing. The fifth drawing is an engineering sectional view of a method of manufacturing a thin film transistor of the fourth drawing. Element symbol description 2, 51, 5 2 Substrate 4 Liquid 6 Flow meter 8 Gas introduction part 10 Nitrogen 2 3 Polycrystalline film 2 5 Isopole electrode 2 7 Dipole range 2 9 interlayer insulating film 3 1 Wiring pattern 4 0 Wiring (display device) 54 halogen electrode 1 reaction chamber 3 platform material tank 5 organic metal material 7 gasifier 9 gas discharge portion 2 2 buffer layer 24 gate insulating film 2 6 source range 28 channel range 3 0 contact hole 3 2 Cu wiring pattern 50 liquid crystal display device

Page 29 1279860 Brief description of the diagram 5 5 thin film transistor 5 7 Signal wiring 5 9 signal wiring terminal 6 1 image signal circuit 5 6 scanning wiring 5 8 scanning wiring terminal 6 0 signal driving circuit 6 2 electrode

Page 30

Claims (1)

1279860 Amendment of the year and month to repair (more) the original method, fly ___character 趸 _ case number 92190011 "一____ 0^^ {\ VI. Patent application scope 1. A metal wiring shape is selective in the selection range Forming a metal wiring; setting an electronegativity of a material constituting the aforementioned selection range to xs; at least in the vicinity of the aforementioned selection range, 'the aforementioned metal matching range is not formed, and the material constituting the non-selected range=non-Xm Note: The electronegativity of the organometallic material belonging to the rifling is set to m, and the relationship of each electrical negative 疋xs &lt;xn&lt;Xm. q 2·Formation of metal wiring as described in the scope of the patent application, characteristics The above-mentioned gold wiring is formed by the heterogeneous reaction of the organic metal material (ldiSPr〇P〇rti〇nation). The metal wiring of the first paragraph of the patent scope of the patent application is the Chigu and the Tugan Temple. The metal wiring is formed by using the above-mentioned organometallic material and the bismuth, octa-Cu film. The pre-milk phase growth method and the fourth embodiment of the invention are characterized in that the composition is Peripheral metal Formation of the line 5. As claimed in the scope of the patent!, 2 or 】:: a conductive material. The method, the special micro-casting,,,, the formation of metal wiring - the formation of nitride The insulating material is oxide or 6 as in the fifth paragraph of the patent application scope, Si3N4 or Al2〇. The insulating material composed of the compound is the 31st page! 279860 Amendment 1 is a manufacturing method of a display device, characterized in that: a plurality of matrix-shaped halogen electrodes are selectively formed in a selected range to form a metal wiring; ^ a plurality of thin film transistors (Film Transistor) each connecting the plurality of halogens An electrode; a plurality of scanning wires and signal wires for driving the thin film transistor; forming a selection range of wirings of at least one of the scanning wiring and the signal wiring, and setting an electrical confinement of a material constituting the selection range to Xs ; the non-selection range of the aforementioned wiring is not formed and the electronegativity of the material constituting the non-selection range is set to χη; and the electronegativity of the organic metal material for forming the wiring is set to Xm, and each electronegativity is X s &lt; X η &lt; X in relationship. 8. The method of manufacturing a display device according to item 7 of the scope of the patent application, characterized in that: The thin film transistor and the pixel electrode are connected by electric wiring, and the selection range of the electric wiring is formed, and the electronegativity of the material constituting the selection range is set to Xs; the non-selection range of the electric wiring is not formed and The electronegativity of the material constituting the non-selected range is Χη; and the electronegativity of the organic metal material for forming the electric wiring is set to 111, and the respective electronegativity is 13 &lt; 111 &lt; 1111. 9. The method of manufacturing a display device according to claim 8, wherein Page 32 1279860 Page 33