METHOD FOR DEPOSITING A MICRON-SIZE METALLIC FILM ON A TRANSPARENT SUBSTRATE UTILIZING A VISIBLE LASER

Abstract: A method for depositing a micron-size metallic film on a transparent substrate by thermal deposition employing a focused visible laser. The method includes the step of positioning the substrate in a gas cell containing a metal bearing gaseous compound. A nucleation layer is formed on a surface of the substrate by either shining an ultraviolet light on the substrate surface or by heating the substrate to a temperature which is less than the temperature at which the molecules of the gaseous compound decompose. Next, a laser which may be visible or near infrared is focused onto the substrate to provide localized heating of the area of the substrate to which the beam is incident. Molecules of the gaseous compound thermally decompose on the heated area to deposit a metal film thereon.

Description: TECHNICAL FIELD The present invention relates to a method for the maskless deposition of a micron-size metallic film on a transparent substrate by thermal deposition utilizing a focused visible laser or rear infrared laser and to such a method for repairing clear defects in photomasks. BACKGROUND OF THE INVENTION Various methods are known for locally depositing a metal film on a transparent substrate, these methods having been used to repair clear defects in photomasks which are used in the manufacture of semiconductor devices. One known method includes the step of depositing a photoresist over the entire surface of the photomask containing the defect. The defective area is then exposed to ultraviolet radiation, after which the photoresist is developed to dissolve the material where it has been exposed to the radiation. The substrate is then placed in a vacuum chamber in which chromium is evaporated to deposit chromium on the surface of the substrate. The photoresist is removed leaving a chromium deposit on the area exposed to the ultraviolet radiation. This method for repairing a photomask is not only time-consuming and of limited resolution, but further results in chromium deposits in undesired areas thus creating additional defects in the photomask which must be removed. One known method for depositing a metal film on a substrate as shown in the U.S. Patent No. 4,340,617 employs an ultraviolet laser which is focused onto a substrate positioned in a gas cell into which metal bearing gases are introduced. The gas absorbs a portion of the laser energy for effecting photodecomposition of the gas near the surface of the substrate to deposit metal material on the substrate. This method is undesirable because ultraviolet laser sources are typically very large in size, bulky and have been found to be unstable when operating continuously for a given period of time. The optics used with such lasers are also very difficult to adjust resulting in problems with focusing and resolution. Further, photodeposition rates are typically low. Another known method for depositing a metal film on a substrate is a laser-induced thermal deposition process. One such process employs a CO₂ laser, generating infrared radiation, to deposit a metal film on a quartz substrate. This method has been found undesirable, however, because the resolution is limited essentially to the wavelength of the radiation; namely, 10.6µm and the complications involving far infrared optics. Another known thermal deposition process employs a visible laser to deposit a metal film on an opaque substrate. Problems have arisen with this process, however, when the visible laser is employed to deposit a metal film on a transparent substrate. It has been found that it takes a very long time to heat a clean transparent substrate to the point at which the metal bearing molecules decompose on the hot substrate surface and stick thereto to form a metal film on the substrate surface. Typically, the visible laser heats the transparent substrate a little, causing the molecules to decompose, however, the metal film does not immediately stick to the substrate but evaporates. After beating the substrate a sufficiently long period of time, on the order of 2-3 Seconds, a metal deposit will form on the substrate surface, the deposit being much larger than the area of the substrate to which the visible laser is incident. There is very little control over the size of metal deposit produced by this method so that the deposits are not reproducible. Further, very small deposits on the order of a micron cannot be made with this method. A method of laser induced chemical vapour deposition of Ni by decomposition of ni (co)₄ is disclosed by W. Krauter et al in Applied Physics A : Solids and surfaces, Vol. A31, No. 1, pp. 13-18 (1983), Springer, Berlin, DE. A nickel stripe of 1.3µm width is deposited on a glass substrate covered with a layer of silicon from a vapour of Ni (CO)₄ by irradiating the substrate with a focussed Kr⁺ laser having a wavelength of 530.9nm. After an initial phase of nucleation the deposition process is thermally activated. A method of laser chemical modification of nucleation barriers for area selective thin film growth is disclosed by J. Y. Tsao and D. J. Ehrlich in Journal of Crystal Growth, Vol. 68, pp. 176-187 (1984), Elseveir Science, Amsterdam, NL. According to the method a 257.2nm Ar⁺ laser beam is used to deposit a 5nm thick Al stripe on a quartz substrate. There is further irradiation using a co₂ laser as a localized heat source resulting a thickening of the stripe to 100nm. A paper by Rytz-Froidevaux in Appl. Phys. A27, 133-138 discloses laser initiated deposition of metals and semiconductors as an attractive alternative to convention lithographic techniques. It describes a Kr laser which is used to irradiate a spot on a quartz substrate. The spot irradiated continuously for a first period of time during which a sort of nucleus layer is produced and a second period of time during which Cd is deposited over the nucleus spot. The first time period is disclosed as lasting from 6 secs to 15 mins depending on laser power density and photon energy. In accordance with the present invention, the disadvantages of prior method for depositing metal films on transparent substrates have been overcome. The present invention provides a method of reproducibly depositing a metal film on the surface of a transparent substrate, comprising: positioning said surface in a cell containing a metal-bearing gaseous compound; a nucleation step; and a metal deposition step; characterised in that said nucleation step consists of forming a nucleation layer of randomly deposited parts of said compound on said surface of the substrate; and in that said deposition step follows said nucleation step and consists of focussing a laser beam having a wavelength of two micrometers or less onto an area of said surface having dimensions of the order of one micrometer, so as to heat said area to thermally decompose molecules of said compound on said area and thereby deposit a metal film thereon. With reference to this application, when the term "infrared laser" is used, it means a laser having a wavelength of 2 µm or less. In carrying out the method of the present invention, a transparent substrate or photomask is positioned in a gas cell containing a metal bearing gaseous compound. A nucleation layer is formed on the substrate surface by shining ultraviolet light thereon or by heating the substrate to a temperature which is less than the temperature at which molecules of the gasesous compound decompose. The nucleation layer thus formed provides sites for future film growth - in effect "seeding" the surface. When a visible laser or laser whose wavelength is less than 2 µm is focused onto the surface, localized heating of the area of the substrate to which the beam is incident results. Molecules of the gaseous compound in the gas cell which randomly strike the heated area decompose. In general, the metal atoms do not stick to the transparent substrate but evaporate. However, an enhancement in sticking probability is observed in the nucleated areas. A metal film is thus formed only in that area of the substrate which was nucleated and to which the laser beam was incident. Furthermore, the nucleation layer allows the location and size of the deposit to be controlled and reproducible so that very small deposits on the order of a micron may be made. The nucleation layer also increases the rate such that it is much greater than the rates of prior thermal deposition and photodeposition techniques. The method of the present invention provides a very durable deposit on the transparent substrate, the deposit being capable of withstanding the standard processes for cleaning photomasks. Further, deposition according to this method does not damage the substrate or photomask so that a metal film deposited on the substrate according to this method may be removed with a laser. This method is also advantageous in that it employs a visible laser which is very stable, easily focused, has a high resolution, and has the potential to be very small and compact as compared to a system based on an ultraviolet laser. These and other objects and advantages of the invention, as well as the details of an illustrative embodiment, will be more fully understood from the following description and the drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram illustrating the step of forming the prenucleation layer on a transparent substrate according to the method of the present invention; and FIG. 2 is a block diagram illustrating the step of depositing a metal film on the substrate utilizing a visible laser according to the method of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION In order to deposit a metal film on a transparent substrate 10 according to the method of the present invention, a surface 12 of the substrate, as shown in FIG. 1, is positioned in a gas cell 14 which contains a metal-bearing gaseous compound 16. The gas cell 14 includes metal end plates 16 and 20. The cell 14 also includes a window 22 which is transparent to light from a source used to form a prenucleation layer on the substrate 10 and to light from a source used for thermal deposition as discussed in detail below. The window 22 may, for example, be made of quartz. The substrate 10 also forms a window of the gas cell 14 with the surface 12, on which a metal deposit is to be made, forming an inner surface of the cell. Other gas cell configurations may be employed to carry out the method of the present invention. For example, the substrate 10 may be suspended within a gas cell or the substrate 10 may replace the window 22 so that a metal deposit can form on an inner surface 24 thereof. The metal-bearing gaseous compound 16 is supplied to the cell 14 by an apparatus 26 which includes a valve or the like to adjust the pressure of the gas. The metal-bearing gas may be a metal alkyl, halide or carbonyl and is preferably an organo-metallic compound which exhibits a sufficiently high vapor pressure and a sufficiently low decomposition temperature, i.e., below 200°C, so as to be suitable for thermal decomposition and deposition on the substrate 10. One preferred compound is W(CO)₆. Another preferred compound is Al(CH₃)₃. After positioning the transparent substrate in the gas cell 14, a nucleation layer is formed on the substrate to seed the surface 12 thereof. The nucleation layer is a random deposit of parts of the gaseous compound 16 on the surface 12 of the substrate, forming one or a few monolayers on the substrate surface which are substantially invisible and removable. One method for forming the nucleation layer employs an ultraviolet light source 28 such as a H g lamp or ultraviolet laser. The ultraviolet light from the source 28 passes through the window 22 and illuminates the entire surface 12 of the substrate 10 to randomly deposit parts of the metal-bearing compound 16 on the substrate surface to form a nucleation layer thereon. Another method for forming the nucleation layer includes the step of heating the gas cell 14 to heat the substrate 10 to a temperature which is less than the temperature at which the molecules of the gaseous compound 16 decompose to randomly deposit parts of the compound 16 on the substrate surface 12. After the nucleation layer is formed, a laser source 30, as shown in FIG. 2, is employed to induce thermal deposition of metal-bearing molecules from the compound 16 on the surface 12 of the substrate 10. It is noted that the laser employed for the thermal deposition process may be either a visible laser or a near infrared laser having a wavelength of 2 microns or less. The visible laser beam or near infrared laser beam from the source 30 is focused by a microscope objective 32 onto the surface of the substrate 10 to provide localized heating of the area of the substrate to which the beam is incident. Molecules of the gaseous compound 16 thermally decompose on the heated area to deposit a metal film thereon, the metal film covering only that area of the substrate to which the laser beam is incident. The nucleation layer formed on the substrate surface 12 serves as a seed for metal-film growth and thus allows the size of the metal deposit to be controlled and reproducible so that very small deposits, on the order of a micron, may be made. The small size of the metal deposit made according to this method is limited only by the optics 32 available to focus the laser beam. Further, the nucleation layer results in a greater deposition rate than has heretofore been possible employing prior thermal deposition and photodeposition techniques. For example, the deposit time for the present method may be much less than one second whereas the deposition time for prior methods is typically on the order of two to three seconds. The deposition rate may further be enhanced by regulating the vapor pressure of the gaseous compound 16. Where the metal-bearing gaseous compound 16 is W(CO)₆ or Al(CH₃)₃, to increase the vapor pressure and thus enhance the deposition rate, the compound may be heated to a temperature between 90°C and 150°C. The method of the present invention for depositing a metal film on a transparent substrate may be used to repair clear defects in a photomask which is formed of a transparent material such as quartz or glass with a metal pattern, usually chrome, formed thereon. The photomask is first positioned in a gas cell, such as the cell 14, with the masked surface forming an inner surface of the cell. A nucleation layer is formed on the chrome-coated surface of the photomask as described above, after which a visible laser or a near infrared laser is focused onto the defective area to heat the area of the photomask which is incident to the laser beam. Molecules of the gaseous compound 16 thermally decompose on the heated area to deposit a metal film on the clear defect of the photomask. The method of the present invention allows the size of the deposit to be controlled and reproducible so that very small deposits, on the order of a micron, may be made on a defective area of a photomask. The deposition method provides a repair which is very durable and capable of withstanding the standard processes for cleaning a photomask. Further, the method for depositing a metal film does not damage the substrate 10 or photomask so that a deposit may be removed if desired. It should be noted that the subject invention comprehends an alternate method to repair clear defects in photomasks. This method may be preferred in some embodiments. In the alternative method, a laser of wavelength 2µm or less is focused on the edge of a metal pattern or line adjacent to the clear defect to be corrected (i.e., the quartz area onto which metal is to be deposited). A deposit is formed on the chrome in the area to which the focused laser was incident. The periphery of this metal deposit serves as the nucleation site for further deposition on the clear defect area (i.e., the quartz area). The laser is moved to this area and a reproducible micron-size deposit is formed. This process is continued until the entire clear defect is covered with metal. The method allows for the controlled growth of micron-size method deposits. In another embodiment, the entire transparent substrate can be heated to just below the thermal decomposition temperature of the gas molecules to aid the laser despotion process A focused laser beam incident on this heated substrate will quickly raise the temperature locally so that gas molecules which randomly strike the area are decomposed leaving behind a metal film deposit. This application is related to our co-pending application published under serial No. 165,686 (claiming priority of U.S. Patent Application Serial No. 622,367) entitled "Method for repairing a Photomask by Laser-Induced Polymer Degradation" and to our co-pending application published under serial No. 165,685 (claiming priority of U.S.Patent Application Serial No. 622,368) entitled "Laser-Based System for the Total Repair of Photomasks." Both of these applications are filed concurrently herewith and are incorporated herein by reference.

Claims: A method of reproducibly depositing a metal film on the surface of a transparent substrate, comprising: positioning said surface in a cell containing a metal-bearing gaseous compound; a nucleation step; and a metal deposition step; characterised in that said nucleation step consists of forming a nucleation layer of randomly deposited parts of said compound on said surface of the substrate; and in that said deposition step follows said nucleation step and consists of focussing a laser beam having a wavelength of two micrometer or less onto an area of said surface having dimensions of the order of one micrometer, so as to heat said area to thermally decompose molecules of said compound on said area and thereby deposit a metal film thereon. A method according to claim 1, wherein: said transparent substrate has a metal pattern formed on said surface. A method according to claim 2, wherein: said substrate and metal pattern comprise a photomask, and said area forms part of or a clear deflect to be repaired by deposition of said metal film. A method according to claim 2 or 3, wherein: said laser beam is focussed on an area of said surface adjacent an edge of said metal pattern. A method according to claim 4, further comprising: moving said laser beam from said edge after said metal film has been deposited to the edge of the deposited film and heating the deposited film to thermally decompose molecules of said compound on the heated film to deposit a metal film thereon. A method according to any of the preceding claims, wherein said nucleation layer is formed by irradiating said surface with ultraviolet radiation so as to randomly deposit parts of said metal-bearing gaseous compound on said surface. A method according to any of the preceding claims wherein said layer is formed by heating said surface to a temperature below that required to thermally decompose said compound before focusing said laser beam to deposit said film. A method according to any of the preceding claims, further including the step of regulating the vapor pressure of said gaseous compound to obtain a deposition time which is substantially less than 10 seconds. A method according to any of the preceding claims, wherein the step of focussing said laser beam includes the step of controlling the growth of the metal deposit on said substrate to provide a micron size metal deposit which is reproducible. A method according to any of the preceding claims, wherein said substrate is made of quartz. A method according to any of the preceding claims, wherein said substrate is made of glass. A method according to any of the preceding claims, wherein said metal-bearing compound is an organometallic compound. A method according to any of claims 1 to 11 wherein said metal bearing compound us a metal alkyl. A method according to any of claims 1 to 11, wherein said metal-bearing compound is a metal halide. A method according to any of claims 1 to 11, wherein said metal-bearing compound is a metal carbonyl. A method according to any of claim 1 to 11, wherein said metal-bearing gaseous compound is A1 (CH₃)₃. A method according to any of claims 1 to 11, wherein said metal bearing gaseous compound is W(CO)₆. A method according to claim 17, further including the step of heating said compound to a temperature between 90°C and 150°C to increase the vapor pressure of the compound and enhance the deposition rate of the metal film on the substrate. A method according to any of the preceding claims in which said laser beam has a wavelength of 2000 nanometers or less. A method according to any of the preceding claims in which said laser beam is visable laser beam. A method according to any of the preceding claims in which said laser beam is an infrared laser beam.

Inventors: BERANEK, MARK W., OPRYSKO, MODEST M.
Applicants: GOULD INC.
Application year: 1985
Main classification: C23C16
IPC codes: H05K3, H01L21, C23C16, G03F1