WO2004073048A2 - Appareil et procede pour produire des films sur des substrats - Google Patents

Appareil et procede pour produire des films sur des substrats Download PDF

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Publication number
WO2004073048A2
WO2004073048A2 PCT/US2003/015952 US0315952W WO2004073048A2 WO 2004073048 A2 WO2004073048 A2 WO 2004073048A2 US 0315952 W US0315952 W US 0315952W WO 2004073048 A2 WO2004073048 A2 WO 2004073048A2
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WO
WIPO (PCT)
Prior art keywords
substrate
films
substrates
samples
liquid
Prior art date
Application number
PCT/US2003/015952
Other languages
English (en)
Other versions
WO2004073048A3 (fr
Inventor
Konstantinos Chondroudis
Eric C. Ramberg
Martin Devenney
Keith Cendak
Sum Nguyen
Qun Fan
Xuejun Wang
Original Assignee
Symyx Technologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/158,375 external-priority patent/US20030224105A1/en
Application filed by Symyx Technologies, Inc. filed Critical Symyx Technologies, Inc.
Priority to AU2003303302A priority Critical patent/AU2003303302A1/en
Publication of WO2004073048A2 publication Critical patent/WO2004073048A2/fr
Publication of WO2004073048A3 publication Critical patent/WO2004073048A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
    • B05C11/02—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface
    • B05C11/08—Spreading liquid or other fluent material by manipulating the work, e.g. tilting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/2813—Producing thin layers of samples on a substrate, e.g. smearing, spinning-on
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00351—Means for dispensing and evacuation of reagents
    • B01J2219/0036—Nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00351—Means for dispensing and evacuation of reagents
    • B01J2219/00364—Pipettes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00277—Apparatus
    • B01J2219/00351—Means for dispensing and evacuation of reagents
    • B01J2219/00387—Applications using probes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00277—Apparatus
    • B01J2219/00351—Means for dispensing and evacuation of reagents
    • B01J2219/00421—Means for dispensing and evacuation of reagents using centrifugation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00351—Means for dispensing and evacuation of reagents
    • B01J2219/00436—Maskless processes
    • B01J2219/00443—Thin film deposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2219/00277—Apparatus
    • B01J2219/00479—Means for mixing reactants or products in the reaction vessels
    • B01J2219/00484—Means for mixing reactants or products in the reaction vessels by shaking, vibrating or oscillating of the reaction vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2219/00277—Apparatus
    • B01J2219/00479—Means for mixing reactants or products in the reaction vessels
    • B01J2219/00488—Means for mixing reactants or products in the reaction vessels by rotation of the reaction vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2219/00277—Apparatus
    • B01J2219/00495—Means for heating or cooling the reaction vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00497—Features relating to the solid phase supports
    • B01J2219/00527—Sheets
    • B01J2219/00536—Sheets in the shape of disks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00585—Parallel processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00659—Two-dimensional arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00675—In-situ synthesis on the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/0068—Means for controlling the apparatus of the process
    • B01J2219/00686—Automatic
    • B01J2219/00691—Automatic using robots
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/0068—Means for controlling the apparatus of the process
    • B01J2219/00702—Processes involving means for analysing and characterising the products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic compounds
    • B01J2219/00747—Catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00756—Compositions, e.g. coatings, crystals, formulations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B12/00—Arrangements for controlling delivery; Arrangements for controlling the spray area
    • B05B12/14—Arrangements for controlling delivery; Arrangements for controlling the spray area for supplying a selected one of a plurality of liquids or other fluent materials or several in selected proportions to a spray apparatus, e.g. to a single spray outlet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B30/00—Methods of screening libraries
    • C40B30/08—Methods of screening libraries by measuring catalytic activity
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B40/00—Libraries per se, e.g. arrays, mixtures
    • C40B40/18—Libraries containing only inorganic compounds or inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B50/00—Methods of creating libraries, e.g. combinatorial synthesis
    • C40B50/14—Solid phase synthesis, i.e. wherein one or more library building blocks are bound to a solid support during library creation; Particular methods of cleavage from the solid support
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
    • C40B60/14—Apparatus specially adapted for use in combinatorial chemistry or with libraries for creating libraries

Definitions

  • the present invention relates generally to the formation of films on one or more substrates for screening and characterization of the film properties, and more particularly to apparatus and methods for forming such films from liquid samples.
  • Combinatorial synthesis and evaluation of arrays of films enables the rapid discovery of new materials with novel chemical and physical properties and the rapid optimization of previously known materials.
  • Such techniques are currently employed to evaluate materials such as superconductors, zeolites, magnetic materials, phosphors, nonlinear optical materials, thermoelectric materials, and high and low dielectric materials.
  • U.S. Patent No. 6,030,917 discloses techniques for the combinatorial synthesis of arrays of organometallic compounds and catalysts. Using the various synthesis methods disclosed therein, arrays containing thousands or millions of different elements can be formed.
  • arrays of materials may be prepared by a variety of techniques, including chemical vapor deposition, physical vapor deposition or liquid dispensing.
  • U.S. Patent Nos. 6,004,617 Schotz et al. and 6,333,196 (Willson et al.) disclose a variety of methods for synthesizing and screening arrays of materials for useful properties.
  • the optimal techniques to apply to array or library design, synthesis, screening and/or informatics may not be straightforward.
  • liquid solution is thus spread over the substrate surface without directly touching the solution, such as with a finger, doctor blade, brush or the like so as to minimize the risk of contaminating the solution.
  • conventional spin-coating techniques are generally disadvantageous for use in synthesizing an array of films, primarily because only a relatively large (e.g., 3-6 inch diameter), single wafer is coated at a time or additional steps, such as masking schemes, must be used.
  • the present invention is generally directed to a method of forming an array of films for use in screening at least one characteristic of at least one of said films.
  • the method comprises the steps of: (i) depositing at least two liquid samples onto at least one substrate such that the at least two liquid samples are at least partially discrete from each other; and, (ii) subjecting the liquid samples to a non-contact spreading force during overlapping durations of time, said spreading force being sufficient to cause each liquid sample to spread over the at least one substrate to form a respective film thereon, at least a portion of each film being discrete from one or more other films formed on said at least one substrate.
  • the present invention is generally directed to a method of forming an array of films for use in screening at least one characteristic of at least one of said firms, the method comprising the steps of: (i) depositing at least two liquid samples onto at least one substrate such that the at least two liquid samples are at least partially discrete from each other; and, (ii) directing a pressurized gas to impact said liquid samples to apply a spreading force thereto sufficient to cause the liquid samples to spread over the at least one substrate surface to form a respective film thereon, at least a portion of each film being discrete from one or more other films formed on said at least one substrate.
  • the present is further directed to an apparatus for forming, and optionally screening, such films.
  • the present invention is in another embodiment directed to an apparatus for forming an array of films on a surface of one or more substrates for use in screening at least one characteristic of at least one of said films.
  • the apparatus comprises: (i) a deposition device adapted for depositing a plurality of liquid samples on the surface of at least one substrate in generally spaced relationship with each other; and, (ii) a movement device capable of supporting the at least one substrate with the liquid samples deposited thereon, said movement device being operable to move the at least one substrate to thereby subject the liquid samples to a spreading force sufficient to cause the samples to spread over the surface of the at least one substrate to form respective films thereon.
  • the present invention is directed to such an apparatus which comprises: (i) a deposition device adapted for depositing a plurality of liquid samples on the surface of at least one substrate in generally spaced relationship with each other; (ii) a support for supporting the at least one substrate; and, (iii) a gas delivery device operable to direct a pressurized gas to impact said liquid samples to thereby cause the liquid samples to spread over the at least one substrate surface to form respective films thereon. Additional features of the present invention will be in part apparent and in part pointed out hereinafter.
  • Fig. 1 is a schematic perspective of a first embodiment of apparatus of the present invention for forming films on substrates
  • Fig. 2 is a photograph of films formed on a substrate using the apparatus of Fig. 1 ;
  • Fig. 3 is side elevation of a movement device of a second embodiment of apparatus of the present invention shown supporting a substrate;
  • Fig. 4 is a top plan view of the movement device of Fig. 3 with the substrate omitted;
  • Fig. 5 is a photograph of films formed on a substrate using the movement device of Fig. 3;
  • Fig. 6 is a perspective of a movement device of a third embodiment of apparatus of the present invention shown supporting a substrate;
  • Fig. 7 is a side elevation thereof with portions omitted to reveal internal construction and with other portions shown in cross-section;
  • Fig. 8 is a photograph of films formed on a substrate using the movement device of Fig. 6;
  • Fig. 9 is a schematic side view of a substrate holder and an air knife of a fourth embodiment of apparatus of the present invention, with the air knife shown in cross-section;
  • Fig. 10 is a top view of the substrate holder and air knife of Fig. 9;
  • Fig. 11 is a side elevation of apparatus of a fifth embodiment of the present invention
  • Fig. 12 is a top plan view thereof of the apparatus of Fig. 11 ;
  • Fig. 13 is a perspective of a portion of the apparatus of Fig. 11 showing a drive system and an array of substrate holders of the apparatus;
  • Fig. 14 is a top plan view of the drive system and substrate holders of Fig. 13;
  • Fig. 15 is a side elevation of the drive system and substrate holders of Fig.
  • Fig. 16 is a cross-section taken in the plane of line 16-16 of Fig. 14 with a control system for the drive system shown schematically;
  • Fig. 17 is a fragmented cross-section of one substrate holder of the apparatus of Fig. 11 ;
  • Fig. 18 is a perspective of one substrate holder driven by a corresponding motor
  • Fig. 19 is an exploded perspective of the substrate holder and motor of Fig. 18;
  • Fig. 20 is a cross-section of an array of substrate holders and a second embodiment of a drive system for the substrate holders;
  • Fig. 21 is a schematic side view of apparatus of a sixth embodiment of the present invention showing a heater for heating substrates on which films are formed.
  • Fig. 22 is a block diagram which illustrates how the methods and apparatus of the present invention may be utilized as part of a system or workflow for the rapid formation of liquid samples and thin films therefrom, as well as to the rapid screening of these films to identify those having desirable properties, all of which may be achieved using combinatorial techniques.
  • Fig. 23 is a block diagram which illustrates some of the various steps that are, or may optionally be, involved in such a system or workflow.
  • apparatus of a first embodiment of the present invention for forming films on substrates is indicated it its entirety by the reference numeral 21.
  • the apparatus 21 is more particularly for forming an array of such films on the surface of a single substrate 23, and even more particularly for the parallel formation of an array of such films on the substrate.
  • the apparatus 21 comprises a deposition device, generally indicated at 25, for depositing one or more liquid samples on the surface of the substrate 23.
  • a movement device, generally indicated at 27, supports the substrate 23 and is capable of moving the substrate to subject the liquid samples to a spreading force, and more particularly to a non-contact spreading force, so as to spread the liquid samples on the substrate and thereby form relatively thin films on the substrate.
  • a non-contact spreading force is defined as a force acting on the liquid samples on the substrate 23 by means other than directly contacting the liquid samples with an implement (e.g., other than the substrate itself), such as a doctor blade or other spreading implement, or with a jetted media.
  • the substrate 23 may be constructed of substantially any material which allows for the formation of films thereon and the subsequent screening of various properties and characteristics of such films.
  • the substrate 23 may be organic, inorganic, biological, nonbiological, or a combination of any of these, and may have any convenient shape, such as a disc, square, sphere, circle, etc.
  • the substrate 23 may be constructed of polymers, plastics, pyrex, quartz, resins, silicon, silica or silica-based materials, carbon, metals, inorganic glasses, inorganic crystals, membranes or other suitable materials which will be readily apparent to those of skill in the art.
  • the substrate 23 has a surface 29 on which the films are to be formed and which may be composed of the same materials as the substrate or, alternatively, the substrate may be coated with a different material to define the exposed substrate surface.
  • the substrate surface 29 may be modified without departing from the scope of the invention.
  • the surface can be rendered hydrophobic, if desired, by treating it with Hexamethyldisilazane (HMDS).
  • HMDS Hexamethyldisilazane
  • the ambient atmosphere could be modified to further affect the liquid solution/substrate interface (e.g., wetting angle).
  • the substrate 23 of the illustrated embodiment is a conventional semiconductor wafer having a surface 29 processed to a mirror-like finish to facilitate uniformity of thickness of the films formed thereon.
  • the substrate surface 29 may have a variety of alternative surface characteristics, depending on the film properties and characteristics to be measured, without departing from the scope of this invention.
  • the substrate surface 29 may have raised or depressed regions on which the synthesis of diverse materials takes place.
  • the wafer shown in Fig. 1 has a diameter of approximately five inches.
  • the size of the substrate 23 may be substantially larger or smaller, such as down to about 0.5 inches, depending on the size and number of films to be formed on the substrate.
  • the deposition device 25 is a robotic device in which a pipette, or probe 31 of the device is manipulated over the substrate surface 29 using a 3-axis translation system.
  • the probe 31 is connected by flexible tubing 33 to one or more sources of liquid from which the films are to be formed.
  • One or more pumps 37 are located along the flexible tubing 33 to draw liquid from the liquid sources and to deliver the liquid to the probe 31. Suitable pumps 37 include peristaltic pumps and syringe pumps.
  • a multi-port valve 39 is disposed in the flexible tubing 33 downstream of the pump(s) 37 to control which liquid is drawn from the liquid sources and delivered to the probe 31 for dispensing onto the substrate 23.
  • each film is desirably sized to have a surface area of at least about 0.1 mm 2 , preferably in the range of about 0.1 mm 2 to about 700 mm 2 , and more preferably in the range of about 1 mm 2 to about 50 mm 2 .
  • the volume of each liquid sample deposited on the substrate surface 29 is preferably in the range of about 0.1 microliters to 10 milliliters, more preferably in the range of about 0.5 microliters to about 500 microliters, still more preferably in the range of about 0.5 microliters to about 100 microliters, even more preferably in the range of about 0.5 microliters to about 50 microliters and most preferably in the range of about 1 microliter to about 10 microliters.
  • the liquid from which each film is formed may be substantially any liquid solution or dispersion from which a film remains upon evaporation of the liquid.
  • the liquid may be a material for which its evaporation, decomposition or otherwise reaction creates films formed of polyimide, silicon dioxide, organic polymers, ceramic materials, composite materials (inorganic composites, organic composites and combinations), photoresists, sol-gel solutions including polymeric metal (organic) oxoalkoxides, other metallo-organic compounds, polymer based light-emitting materials including plastic, solutions and suspensions of ferroelectric materials, and optical coatings.
  • the liquid may also comprise biological materials including antibodies, antigens, DNA, RNA, proteins, enzymes, oligopeptides, polypeptides, oligosaccharides, mono and polysaccharides, and lipids.
  • each film formed on the substrate surface 29 is preferably in the range of about 50 ⁇ to about 1000 micrometers, and more preferably in the range of about 1 ,000 A to about 10 micrometers, and even more preferably in the range of about 1 ,000 A to about 10,000 A.
  • a portion of the surface area of each film formed on the substrate 23 has a substantially uniform thickness to facilitate more accurate screening of the film.
  • a portion of each film preferably has a thickness which is uniform to within a variation of about 0% to about 20%, more preferably to within a variation of about 0% to about 10%, still more preferably to within a variation of about 0% to about 5% and most preferably to within a variation of about 0% to about 3%.
  • the size (e.g., surface area) of a region within each film formed on the substrate surface 29 is preferably at least about equal to the minimum size required by the measurement method used to characterize the film, and is more preferably up to about three times larger than the minimum size required by the measurement method.
  • one preferred spin-coating device 27 is available from Laurell Technologies Corporation of Pennsylvania under the model designation WS- 400A-6NPP.
  • the cylindrical housing 51 has an internal diameter of about 8.5 inches and a height of about 12 inches.
  • a closure 55 is hinged to the housing 51 to permit closing of the housing during operation of the device 27.
  • the chuck 53 of the illustrated embodiment is a vacuum chuck in fluid communication with a vacuum source (not shown) for suctioning the substrate 23 down against the chuck during operation of the spin-coating device 27.
  • a vacuum source not shown
  • the substrate 23 may be supported on the drive shaft by means other than a vacuum chuck, such as by mechanical retainers (not shown) or other suitable means without departing from the scope of this invention.
  • a control system 57 is in electrical communication with the spin-coating device 27 for controlling operation thereof.
  • the control system 57 is preferably a computer based system capable of sending data to and receiving data from the spin-coating device 27 to monitor and control operation of the device.
  • data preferably include a motor start time, rotational acceleration and speed, duration of motor operation and other relevant parameters.
  • the control system 57 is also desirably programmable to permit a pre-determined parameter profile, such as a rate of acceleration, duration of operation, rotational speed and stop time to be pre-programmed.
  • control system 57 may be programmed such that following deposition of one or more liquid samples on the substrate 23, the substrate is subjected to rotation for an initial time period, such as about 5 - 10 seconds, at a relatively low rotational speed, such as about 500 rpm, to promote spreading of the liquid samples on the substrate surface 29.
  • the substrate 23 may then be accelerated to a higher rotational speed, such as about 2000 rpm for a longer duration, such as about 40 seconds, to promote further evaporation of the liquid. It is believed that the hardware and software components of the control system 57 will be readily apparent to those of ordinary skill in this field and therefore will not be described in more detail.
  • a heater (not shown in Fig. 1 but similar to a heater 353 shown in Fig. 21 and described later herein), may be positioned above the substrate 23 in opposed relationship with the substrate surface 29, such as at a distance of about 1 mm up to about 100 mm, to heat the substrate, ambient environment and/or liquid samples deposited on the substrate 23 during operation of the spin-coating device 27.
  • the heater is preferably capable of generating heat at a temperature in the range of about 25°C to about 500°C, more preferably in the range of about 50°C to about 450°C, and most preferably in the range of about 100°C to about 400°C.
  • one preferred such heater is a flat panel infrared heater available from Ogden of Arlington Heights, Illinois under the model designation FP2017 and is operable to generate heat at a temperature of up to about 200°C.
  • a cooling device (not shown) may be used to cool the substrate, ambient environment and/or liquid samples without departing from the scope of this invention.
  • a substrate 23 is secured to the chuck 53 of the spin-coating device 27 generally coaxially with the rotation axis of the device and with the mirror-finish surface of the substrate exposed (e.g., facing up as shown in Fig. 1 ).
  • the deposition device 25 is then operated to deposit one or more liquid samples on the exposed substrate surface 29.
  • the samples may be deposited serially, such as by the device 25 shown in Fig. 1 , or simultaneously, such as by a deposition device (not shown) having multiple probes.
  • liquid sample if only one liquid sample is deposited on the substrate surface 29, it may be located offset from the center of the substrate 23 (e.g., relative to the rotation axis of the spin-coating device). In the event more than one liquid sample is deposited on the substrate 23, the liquid samples are preferably deposited thereon in spaced relationship with each other, with the samples all being generally offset from the center of the substrate or with one of the samples being deposited at the center of the substrate.
  • the spin-coating device 27 is then operated to rotate the substrate 23 on the rotation axis of the device. The rotation of the substrate 23 subjects the liquid samples on the substrate surface 29 to a non-contact spreading force, resulting in a shear stress at the liquid sample/substrate surface interface.
  • portions of adjacent films may overlap each other and remain within the scope of this invention, as long as a portion of each film remains sufficiently discrete from other films on the substrate surface to permit the desired screening of each different film.
  • an area of at least about 0.1 mm 2 of each film formed on the substrate 23 is preferably discrete from other films formed thereon.
  • certain experimental designs may require overlap between films, e.g., to investigate multilayer phenomena.
  • the liquid samples may alternatively be deposited onto the substrate surface 29 during operation of the spin-coating device 27 so that the substrate surface is already rotating as liquid samples are deposited thereon.
  • Example 1 The above method was used to form a plurality of silica-based films for the evaluation of their dielectric, optical, mechanical and chemical properties.
  • a liquid solution comprising a silica source, a catalyst, a surfactant and a solvent was prepared and used as a liquid source for the deposition device 25 of Fig. 1.
  • a silicon wafer having a diameter of about three inches was suctioned down against the vacuum chuck of the spin-coating device 25 of Fig. 1.
  • the deposition device 25 was operated to serially dispense thirteen liquid samples of the solution on the exposed surface 29 of the wafer in a generally circular pattern having a diameter of about two inches, with the center-to-center spacing between adjacent samples being about 8 mm.
  • the volume of each liquid sample was in the range of about 2-5 microliters.
  • the control system 57 was used to operate the spin-coating device 27 according to a predetermined program pursuant to which after the deposition of each sample of liquid on the substrate 23, the substrate was rotated at an acceleration rate of about 2000 rpm/sec until the rotational speed reached about 3000 rpm (e.g., about 1.5 seconds), and rotation then continued at a speed of 3000 rpm for about 5 - 10 seconds.
  • the control system 57 then caused rotation of the substrate 27 to stop while another sample of liquid was deposited on the substrate surface 29.
  • Rotation of the substrate 23 subjected the liquid samples to a non-contact spreading force, resulting in the liquid samples spreading radially and tangentially outward on the wafer surface to form films thereon.
  • Figure 2 illustrates the pattern of corresponding films F formed on the wafer surface 29.
  • a movement device 27 of a second embodiment of apparatus 21 of the present invention is shown in Figs. 3 and 4.
  • the movement device 27 is an oscillatory movement device, and more particularly an orbital movement device capable of oscillating the substrate 27 along an orbital path.
  • the orbital movement device 27 comprises a housing 61 and an orbital drive system (not shown) operatively connected to an orbiting member (Fig. 3) for driving eccentric orbital movement of the orbiting member.
  • the orbiting member 27 of the illustrated embodiment extends up out of the housing 61 and has a substrate holder 65 mounted thereon for conjoint orbital movement with the orbiting member.
  • General construction and operation of orbital movement devices is known in the art and will not be further described herein except to the extent necessary to describe the present invention.
  • one preferred orbital movement device 27 is available from IKA-Works, Inc. of Wilmington, N.C., U.S.A., under the model designation MS1 MINISHAKER.
  • the device 27 is capable of driving orbital movement of the substrate holder 65 (and hence the substrate 23 supported by the holder 65) at a speed in the range of about 200 rpm to about 2500 rpm along an eccentric path of up to about 0.177 inches on a major axis and up to about 0.089 inches on a minor axis.
  • the holder 65 comprises a base 67 adapted for connection with the orbiting member 19, and three arms 69 (Fig.
  • the base 67 of the holder 67 includes a skirt 75 formed integrally therewith and depending therefrom.
  • the skirt 75 is tapered in accordance with the contour of the housing 61 to generally surround and shield the portion of the orbiting member 63 which extends outward of the housing.
  • the arms 69 of the holder 67 are preferably in equiangular relationship with respect to one another (e.g., at angles of about 120° relative to each other).
  • a retainer in the form of a pin 73 extends up from the upper surface of each arm 69 generally adjacent its outer end.
  • the substrate 23 thus seats on the upper surfaces of the arms 69 with the peripheral edge of the substrate 23 generally centered within the pins 73 such that the pins inhibit lateral (e.g., sliding) movement of the substrate on the holder during operation of the orbital movement device 23.
  • the apparatus 21 of this second embodiment may also have a control system (not shown but similar to the control system 57 shown in Fig. 1 ) for controlling the drive system of the orbital movement device 27.
  • the control system 57 may be used to monitor and control the drive system start time, the orbital path and speed of the device, the duration of operation of the drive system and other relevant parameters.
  • a heater not shown but similar to the heater 353 shown in Fig. 21 and described later herein
  • a cooling device may be used to heat or cool the substrate 23 and/or liquid samples during operation of the orbital movement device 27.
  • the substrate 23 is placed in the holder 65 of the orbital movement device 27 as described above, with the mirror-finish surface 29 exposed (e.g., facing up in the device of Fig. 3).
  • the deposition device 25 is then operated to deposit one or more liquid samples on the exposed substrate surface 29.
  • the liquid samples may be deposited onto the substrate surface 29 serially, such as by the device shown in Fig. 1 , or simultaneously, such as by a deposition device (not shown) having multiple probes. It is contemplated that if only one liquid sample is deposited on the substrate surface 29, it may be located offset from the center of the substrate 23.
  • the liquid samples are preferably deposited thereon in spaced relationship with each other, with the samples all being generally offset from the center of the substrate or with one of the samples being deposited at the center of the substrate.
  • the orbital movement device 27 is then operated to drive movement of the substrate 23 along an orbital path. Orbital movement of the substrate 23 subjects the liquid samples on the substrate surface 29 to a non-contact spreading force, resulting in a shear stress at the liquid sample/substrate surface interface. When sufficiently large, this shear stress causes the liquid samples to spread or flatten on the substrate surface 29 to facilitate thinning of the liquid and evaporation thereof to thereby form corresponding thin films on the substrate surface.
  • orbital movement of the substrate 23 by the orbital movement device 27 of the illustrated embodiment causes each liquid sample to spread or flatten on the substrate surface 29 in a generally circular pattern to form generally circular films F on the substrate in Fig. 5.
  • the liquid samples are preferably deposited on the substrate surface 29 with sufficient spacing there between such that the films F formed on the substrate surface remain discrete from each other.
  • portions of adjacent films may overlap each other and remain within the scope of this invention, as long as a portion of each film remains sufficiently discrete from other films on the substrate surface 29 to permit the desired screening of each different film.
  • an area of at least about 0.1 mm 2 of each film formed is preferably discrete from other films formed on the substrate 23.
  • the liquid samples may alternatively be deposited onto the substrate surface 29 during operation of the orbital movement device 27 so that the substrate surface is already moving as liquid samples are deposited thereon.
  • Example 2 The apparatus 21 of the second embodiment was used to form a combinatorial array of silica-based films F for the evaluation of their dielectric, optical, mechanical and chemical properties.
  • Different compositions of a liquid solution comprising a silica source, a catalyst, a surfactant and a solvent were prepared and used as liquid sources for the deposition device 25 (Fig. 1).
  • a silicon wafer having a diameter of about 125 mm was placed in the holder 65 of the orbital movement device 27 of Fig. 3 in the manner described previously.
  • the orbital movement device 27 was operated to move the wafer at a speed of about 2200 rpm along an orbital path having a major axis of about 4.5 mm and a minor axis of about 2.25 mm.
  • the deposition device 25 was operated to serially dispense twenty-five samples of liquid on the wafer in a generally square pattern (e.g., a matrix of five rows of five samples each), with the center-to-center spacing between adjacent samples being about 17.5 mm.
  • the volume of each liquid sample was in the range of about 2-5 microliters.
  • Dispensing of the liquid samples on the wafer occurred over a period of about 12 minutes, and the substrate 12 was moved on its orbital path for a total duration of about 15 minutes (e.g., about 3 minutes longer than the time at which the last liquid sample is deposited on the substrate), after which orbital movement of the substrate was stopped.
  • Figure 5 illustrates the pattern of corresponding films F formed on the wafer surface 29.
  • the diameter of each of the films formed on the wafer surface 29 was approximately 17 mm.
  • Figures 6 and 7 illustrate a movement device 27 of a third embodiment of apparatus 21 of the present invention in which the movement device subjects the substrate to oscillatory movement.
  • the movement device 27 is a reciprocating device and, more particularly, a linear reciprocating device capable of reciprocating the substrate 23 along a longitudinal path extending generally normal to the surface 29 of the substrate (e.g., up/down as indicated by the direction arrow in Fig. 6).
  • the linear reciprocating device 27 generally comprises a housing 81 , a drive system generally indicated at 83 in Fig. 7, and a holder, generally indicated at 85, operatively secured to the drive system for supporting the substrate 23 during operation of the device.
  • the drive system 83 of the illustrated embodiment is an electromagnetic drive system including an armature 87 coaxially received within a central passage of an electromagnetic coil 89.
  • the armature 87 is movable axially (e.g., vertically) relative to the coil 89 on along a longitudinal path defined by the armature.
  • Leaf springs 91 are secured to the armature 87 toward its upper end for controlling the axial displacement of the armature.
  • the drive system 83 also includes a generally rectangular mounting block 93 secured to the top of the armature 87 for conjoint linear reciprocation therewith.
  • a cover plate 95 is secured to the top of the mounting block 93 for conjoint movement therewith and generally defines the top of the housing 81.
  • linear reciprocation devices such as the device 27 described herein and illustrated in Fig. 7 as having an electromagnetic drive system 83
  • an electromagnetic drive system 83 General construction and operation of linear reciprocation devices such as the device 27 described herein and illustrated in Fig. 7 as having an electromagnetic drive system 83 is known in the art and will not be further described herein except to the extent necessary to describe the present invention.
  • U.S. Patent Nos. 3,155,853 and 4,356,911 disclose reciprocating devices having electromagnetic drive systems.
  • One particularly preferred linear reciprocation device 27 is available from Union Scientific Corporation of Randallstown, Maryland, U.S.A., as a vertical electromagnetic shaker.
  • the drive system 83 is capable of linear reciprocation at a frequency of up to about 60 Hz and an amplitude of up to about 0.15 inches.
  • the holder 85 comprises a support platform which, in this embodiment, comprises a plate 97 secured to the cover plate 95 and having a depression, or seat 99, formed in its upper surface for receiving the substrate 23 therein.
  • the seat 99 has a size and shape closely conforming to the size and shape of the substrate 23 to provide a close clearance fit of the substrate 23 in the seat.
  • a groove 101 is formed within the upper surface of the support plate 97 and extends from the seat 99 out to the peripheral edge of the support plate to facilitate handling of the substrate 23, such as lifting the substrate out of the seat.
  • a pair of retaining arms 103 is secured to the upper surface of the support plate 97 in spaced relationship with each other adjacent the peripheral edge of the seat 99.
  • Each retaining arm 103 is pivotally secured at a pivot end 105 thereof to the upper surface of the support plate 97 by a suitable fastener 107.
  • An opposite, free end 109 of each retaining arm 103 has an open slot 111 formed therein which is sized for receiving another fastener 113.
  • a central portion 115 of each retaining arm 103 is configured for extending over the peripheral edge margin of the seat 99 (and hence the substrate 23 seated therein) and has a thickness such that the retaining arm engages the substrate to urge the substrate down into the seat during operation of the device 27.
  • the fasteners 113 at the free ends 109 of the arms 103 are loosened and the arms are pivoted out to an open position (e.g., as shown by one arm in Fig. 6) in which the arms do not extend over any portion of the seat 99 formed in the upper surface of the support plate 97.
  • the substrate 23 is then placed in the seat 99 and the arms 103 are pivoted inward to a closed position (e.g., as shown by the other arm in Fig. 6) in which the shafts of the loosened fasteners 113 are received in the slots 111 formed in the free ends 109 of the arms 103.
  • the central portions 115 of the retaining arms 103 extend over a peripheral edge margin of the seat in engagement with the substrate 23 seated therein.
  • the fasteners 113 at the free ends 109 of the arms 103 are then tightened, causing the central portions 115 of the retaining arms 103 to generally urge the substrate 23 down into the seat 99 to inhibit movement of the substrate during operation of the device 27.
  • linear reciprocation of the substrate 23 along a path normal to the substrate surface 29 may be performed with other conventional linear reciprocating devices having drive systems other than an electromagnetic drive system.
  • movement devices capable of reciprocating the substrate along an axis other than normal to the substrate surface are known in the art and may be used without departing from the scope of this invention.
  • a movement device in which the substrate is reciprocated generally in the plane of the substrate surface e.g., side-to-side
  • Devices in which a combination of reciprocating movements within and out of the plane of the substrate supported thereby such as a device in which the substrate is rocked back and forth on an arcuate path, may be used.
  • a movement device in which the substrate is rotated such as the spin-coating device of Fig. 1
  • the movement device 27 may also move the substrate 23 in different ways, either sequentially or concurrently, such as by reciprocating the substrate up and down while the substrate is moved in an orbital path or rotated, or by varying the operating parameters of the movement device, such as to vary the speed (e.g. rotational speed or frequency) or displacement (e.g., amplitude or orbital path) of the substrate, during operation of the device.
  • the apparatus 21 of this third embodiment may also comprise a control system (not shown but similar to the control system 57 shown in Fig. 1 ) for controlling the drive system of the reciprocating movement device 27.
  • the control system may be used to monitor and control the drive system 83 start time, the amplitude and frequency of the device, the duration of operation of the drive system and other relevant parameters.
  • a heater not shown but similar to the heater 353 shown in Fig. 21 and described later herein
  • a cooling device may be used to heat or cool the substrate 23 and/or liquid samples during operation of the reciprocating movement device 27.
  • a substrate 23 is seated in the holder 85 of the linear reciprocating device 27 in the manner described previously, with the mirror-finish surface 29 of the substrate exposed (e.g., facing up in the device shown in Fig. 6).
  • the deposition device 25 is then operated to deposit one or more liquid samples on the exposed substrate surface 29.
  • the liquid samples may be deposited serially, such as by the device 25 shown in Fig. 1 , or simultaneously, such as by a deposition device (not shown) having multiple probes. It is contemplated that if only one liquid sample is deposited on the substrate surface 29, it may be located offset from the center of the substrate.
  • the liquid samples are preferably deposited thereon in spaced relationship with each other, with the samples all being generally offset from the center of the substrate or with one of the samples being deposited at the center of the substrate.
  • the reciprocating movement device 27 is then operated to effect a linear reciprocating movement of the substrate 23, such as up and down for the device shown in Fig. 6.
  • Linear reciprocation of the substrate 23 subjects the liquid samples to a non-contact spreading force (e.g., due to acceleration), resulting in a shear stress at the liquid sample/substrate surface interface.
  • this shear stress causes the liquid samples to spread or flatten on the substrate surface 29 to facilitate thinning of the liquid and evaporation thereof to thereby form corresponding thin films on the substrate surface.
  • Linear reciprocation of the substrate 23 facilitates a more controlled spreading or flattening of the liquid sample on the substrate surface 29.
  • the vertical reciprocating movement of the substrate by the device 27 of the illustrated embodiment causes each liquid sample to spread or flatten on the substrate surface 29 in a generally circular pattern to form generally circular films F on the substrate 23, as shown in Fig. 8.
  • the liquid samples are preferably deposited on the substrate surface 29 with sufficient spacing there between such that the films formed on the substrate surface remain discrete from each other.
  • portions of adjacent films may overlap each other and remain within the scope of this invention, as along as a portion of each film remains sufficiently discrete from other films on the substrate surface 29 to permit the desired screening of each different film.
  • an area of at least about 0.1 mm 2 of each film formed on the substrate surface 29 is preferably discrete from other films formed thereon.
  • the liquid samples may alternatively be deposited on the substrate surface 29 during operation of the reciprocating movement device 27 so that the substrate surface 29 is already moving as liquid samples are deposited thereon.
  • Example 3 The apparatus 21 of the third embodiment was used to form a combinatorial array of silica-based films. Different compositions of a liquid solution comprising a silica source, a catalyst, a surfactant and a solvent were prepared and used as liquid sources for the deposition device (Fig. 1 ). A silicon wafer having a diameter of about 125 mm was placed in the holder 85 of the reciprocating movement device 27 of Fig. 6 in the manner described previously. The reciprocating movement device 27 was operated to reciprocate the wafer along a linear path normal to the wafer surface 29 at an amplitude of about 0.07 inches and at a frequency of about 60 Hz.
  • the deposition device 25 was operated to serially dispense twenty-five samples of liquid on the wafer in a generally square pattern (e.g., a matrix of five rows of five samples each), with the center-to-center spacing between adjacent samples being about 17.5 mm.
  • the volume of each liquid sample was in the range of about 2-5 microliters.
  • Dispensing of the liquid samples on the wafer occurred over a period of about 12 minutes, and the wafer was reciprocated for a total duration of about 15 minutes (e.g., about 3 minutes longer than the time at which the last liquid sample is deposited on the substrate 23), after which movement of the substrate was stopped. Linear reciprocating movement of the wafer caused the liquid samples to spread over the wafer surface 29 to form films thereon.
  • Figure 8 illustrates a pattern of corresponding films F formed on the wafer surface.
  • the diameter of each of the films formed on the wafer surface was approximately 17 mm.
  • each of the films formed as a result of the vertical reciprocating movement has a generally concave cross section, with the center portion of the film being thinner than an annular area of the film toward the peripheral edge thereof.
  • FIGS 9 and 10 illustrate a portion of a fourth embodiment of apparatus 21 of the present invention in which a spreading force is applied to the liquid samples by pressurized gas, such as air, directed toward the substrate 23 by an air knife (broadly, a gas delivery device), generally indicated at 121.
  • the substrate 23 is supported by a suitable holder 123 mounted on a stand 125, and the air knife 121 is positioned above the substrate at a distance of from about 1 mm up to about 100 mm.
  • the air knife 121 comprises a manifold 127 in fluid communication with a source (not shown) of pressurized gas via a suitable gas line 129, and one or more nozzles 131 (two are shown in Fig. 10) secured to the manifold for receiving pressurized gas and directing the gas down toward the substrate surface.
  • Gas supplied to the nozzle(s) 131 is preferably at a pressure in the range of from about 1 psi to about 100 psi, and more preferably in the range of about 5 psi to about 20 psi.
  • the nozzles 131 are preferably oriented to direct pressurized gas down toward the substrate surface 29 at an impact, or incident angle in the range of about 0° to about 90°, more preferably in the range of about 10° to about 80°, and most preferably in the range of about 30° to about 60°.
  • General construction and operation of air knives is known in the art and will not be further described herein except to the extent necessary to describe the present invention.
  • one preferred air knife 121 is available from Silvent of Sweden under the model designation 392 and comprises a pair of generally flat nozzles.
  • Other conventional air knives 121 are shown and described in U.S. Patent Nos. 2,135,406 and 5,505,995.
  • the air knife 121 may be moveable relative to the substrate 23 during operation of the air knife to vary the direction at which air impacts the substrate surface (and hence the liquid samples deposited thereon).
  • the substrate 23 may be moveable instead of, or in addition to, the air knife 121 , such as by being rotated or moved laterally relative to the air knife, without departing from the scope of this invention.
  • a substrate 23 is supported by the holder 123 with the mirror- finish surface 29 of the substrate exposed (e.g., facing up in the device 27 shown in Fig. 9).
  • the deposition device 25 is then operated to deposit one or more liquid samples on the exposed substrate surface 29.
  • the liquid samples may be deposited serially, such as by the device shown in Fig. 1 , or simultaneously, such as by a deposition device having multiple probes. It is contemplated that if only one liquid sample is deposited on the substrate surface 29, it may be located offset from the center of the substrate. In the event more than one liquid sample is deposited on the substrate surface 29, the liquid samples are preferably deposited thereon in spaced relationship with each other, with the samples all being generally offset from the center of the substrate or with one of the samples being deposited at the center of the substrate.
  • the air knife 121 is then operated to direct pressurized gas toward the substrate surface 29 to impact the liquid samples.
  • the pressurized gas impacting the liquid samples subjects the liquid samples to a spreading force, resulting in a shear stress at the liquid sample/substrate surface interface.
  • this shear stress causes the liquid samples to spread or flatten on the substrate surface 29 to facilitate thinning of the liquid and the gas flow further facilitates evaporation of the liquid samples to thereby form corresponding thin films on the substrate surface.
  • the liquid samples are preferably deposited on the substrate surface 29 with sufficient spacing there between such that the films formed on the substrate surface remain discrete from each other.
  • portions of adjacent films may overlap each other and remain within the scope of this invention, as along as a portion of each film remains sufficiently discrete from other films on the substrate surface 29 to permit the desired screening of each different film.
  • an area of at least about 0.1 mm 2 of each film formed on the substrate surface 29 is preferably discrete from other films formed thereon. It is contemplated that liquid samples on the substrate 23 may be subjected to non-contact spreading forces other than by the movement devices 27 described previously or by the air knife 121 without departing from the scope of this invention.
  • liquid samples may be dispensed onto the substrate 23 and the substrate may be tilted, or the substrate may be tilted prior to the delivery of liquid samples thereon, such that the liquid samples on the substrate are subjected to a gravitational force sufficient to spread the liquid samples on the substrate surface 29.
  • the tilt of the substrate 23 may also be varied as the liquid samples spread over the substrate surface 29.
  • the substrate may be moved, such as by the movement devices 27 described previously, or by the air knife 121 , concurrently with tilting the substrate.
  • Figs. 11-19 illustrate yet another embodiment of apparatus of the present invention for forming films on substrates.
  • the aforementioned drive system 253 is mounted on a frame having a base 257, side walls 259 extending up from the base, and a top wall 261 which spans the side walls (Fig. 13).
  • the drive system 253 includes at least one and preferably a plurality of electric motors 263, one per substrate 223, mounted below the top wall 261 of the frame by suitable fasteners.
  • An output shaft 265 of each motor 263 projects up into a hole 267 through the top wall 261 of the frame and is connected to a respective substrate holder 251 by a shaft assembly comprising a cylindric rotor and drive shaft designated 269 and 271 , respectively.
  • the rotor 269 is secured, as by a press fit, on the output shaft 265 of the motor 263 and has an outside dimension smaller than the hole 267 in the top wall 261 to provide the clearance necessary for the rotor to freely rotate as it is driven by the output shaft 265 of the motor.
  • the drive shaft 271 has a lower end 273 of reduced diameter press fit (or otherwise secured) in the upper end of the rotor 269 and an upper end 275 of reduced diameter formed with a bore 277 which extends down into the body of the drive shaft.
  • the drive shaft 271 , rotor 269 and output shaft 265 of the motor 263 preferably have a common vertical axis of rotation.
  • the spacing between adjacent motors 263 and drive shaft assemblies will depend primarily on the size of the holders 251 , which in turn will depend on the size of the substrates 223 to be held by the holders.
  • the centerline spacing between adjacent drive shafts 271 is preferably in the range of about 1 mm to about 500 mm, more preferably in the range of about 10 mm to about 100 mm, and even more preferably in the range of about 20 mm to about 80 mm.
  • the construction of the drive shaft assembly may vary.
  • the rotor 269 and drive shaft 271 could be formed as a single piece, or as more than two pieces.
  • each motor 263 can also be relatively small.
  • each motor 263 may be a DC electric motor having a power output of about 3.5 W, a maximum speed of about 7000 rpm, a continuous torque of about 4.95 mNm and a stall torque of about 15.5 mNm.
  • Other types of motors may also be used.
  • each substrate holder 251 has a base 281 with openings 283 therein adjacent the periphery of the base, a circular rim 285 extending up from the base, and a recess 287 or depressed area in the upper surface of the base for receiving a substrate 223 therein.
  • the recess 287 is sized and shaped to hold the substrate 223 in a substantially fixed position against lateral movement during rotation of the drive shaft 271.
  • a central hub 289 projects down from the base 281 generally co-axially with respect to the respective drive shaft assembly.
  • the hub 289 and drive shaft 271 are removably and drivingly connected by a connector 291 having an enlarged upper end received and secured (as by a press fit) in an opening in the hub and a lower end received and secured (as by a press fit) in the bore 277 in the drive shaft.
  • the connector 291 is formed with one or more keys 293 receivable in keyway slots 295 extending down from the upper end 275 of the drive shaft 271 to prevent relative rotation of the drive shaft and the connector.
  • the construction of the holder 251 and connector 291 may vary.
  • the holders 251 may have a construction similar to that of the holders 53, 65, 85, 123 of the various embodiments discussed above.
  • the substrates 223 are typically held in their respective seats by gravity and friction. Where necessary, other mechanisms can be used, such as vacuum, mechanical retainers, or other suitable means.
  • the number of substrate holders 251 and substrates 223 in the array may range from 2 to 96 or more.
  • the configuration of the array may also vary.
  • the array shown in the drawings includes eight holders 251 and associated components, all arranged in the form of a 1 x 8 matrix.
  • the holders 251 could be arranged in a matrix having any number of columns and rows, or they could be arranged in a geometric formation (e.g., a circle), or even randomly, without departing from the scope of this invention.
  • the substrate holders 251 (and substrates 223 therein) be relatively closely spaced in an array which occupies an area (i.e., footprint) having a maximum dimension of less than about five feet by five feet, and more preferably occupies an area of about 1000 mm by about 300 mm, and even more preferably an area of about 100 mm by about 30 mm.
  • the array should be confined to an area capable of being servi ci ed by the robot system.
  • the footprint of the array shown n Fig. 13 is generally rectangular, having a length of about 300 mm and a wi di th of about 125 mm.
  • the drive system 253 could have configurations other than those described above without departing from the scope of this invention.
  • the motors 263 could be mounted on multiple frames instead of a single common frame. Further, the motors 263 can be mounted so that their axes are other than vertical.
  • a single motor 263 can also be used to move more than one substrate 223, as exemplified by the system 253 shown in Fig. 20.
  • a single motor 263 is drivingly connected to more than one (e.g., all) of the drive shaft assemblies, as by a gear 301 on the corresponding drive shaft 271 in mesh with a gear train comprising a plurality of gears 303 attached to the remaining drive shafts.
  • the drive shafts 271 are rotatably supported by suitable bearings 297 in the frame.
  • the arrangement is such that rotation of the drive shaft 271 by the motor 263 causes the other drive shafts and associated holders 251 to rotate in unison.
  • the drive system 253 can be operable to move the holders 251 in ways other than uni-directional movement.
  • other drive mechanisms can be employed to effect oscillatory movement, such as orbital movement, reciprocating movement (linear or otherwise) or rocking movement, or other forms of movement effective for subjecting liquid samples on the substrates 223 to non-contact spreading forces.
  • an array of holders 251 mounted on a common frame may be operably secured to the orbiting member of an orbital movement device similar to that shown in Figs.
  • each holder 251 can be mounted on a separate orbital movement device.
  • the drive system 253 can also be operable to move two or more of the substrates 223 in different ways, such as through different types of movement (e.g., rotational, orbital, linear) or at different rates and displacements.
  • the control system 255 for controlling the drive system 253 is preferably a computer based system capable of sending data to the drive system and receiving data from the drive system to monitor and control the operation of the system. Such data preferably includes, for each motor 263, a motor start time, amplitude and/or frequency of movement, duration of motor operation, and any other relevant parameters.
  • the control system 255 is also programmable to permit a pre-determined parameter profile, such as a rate of acceleration, duration of operation, rotational speed and stop time to be pre-programmed.
  • a pre-determined parameter profile such as a rate of acceleration, duration of operation, rotational speed and stop time
  • the control system 255 may be programmed such that following deposition of one or more liquid samples on each substrate 223, the particular substrate is subjected to rotation for an initial time period, such as about 5 - 10 seconds, at a relatively low rotational speed, such as about 500 rpm, to promote spreading of the liquid samples on the substrate.
  • the substrate 223 may then be accelerated to a higher rotational speed, such as about 2000 rpm for a longer duration, such as about 40 seconds, to promote further evaporation of the liquid.
  • the system 255 can be used to control the operation of each motor 263 independent of the operation of the other motors (if more than one motor is used), so that different substrates 223 can be subjected to different movement conditions during the same run of experiments occurring during overlapping durations of time. It is believed that the hardware and software components of the control system 255 will be readily apparent to those of ordinary skill in this field and therefore will not be described in more detail. Liquid samples may be deposited on the substrates 223 manually, or more preferably, by the robotic deposition system 225. It is also contemplated that a robotic system (not shown) may be provided for automatically (instead of manually) mounting the substrates 223 on and removing the substrates from the substrate holders 251 without departing from the scope of this invention.
  • Liquid solutions comprising a silica source, a catalyst, a surfactant and a solvent were prepared and used as liquid sources on the deposition device 25 of Fig. 1.
  • Square silicon wafers each having a length and width of about 0.5 inches (e.g., a surface area of about .25 in. 2 ) were individually placed in each of the eight substrate holders 251 of the apparatus 221 of Fig. 11.
  • the deposition device 25 was operated to dispense a sample of liquid generally centrally on one of the wafers. The volume of the liquid sample was approximately 10 microliters.
  • the control system 255 was used to operate the motor 263 corresponding to the wafer on which the liquid sample was dispensed according to a predetermined program pursuant to which the wafer was rotated at an acceleration rate of about 2000 rpm/sec until the rotational speed reached about 3000 rpm (e.g., about 1.5 seconds), and rotation then continued at a speed of 3000 rpm for about 5 - 10 seconds. Rotation of the wafer subjected the liquid sample to a non-contact spreading force, resulting in the liquid sample spreading out over the wafer surface to form a film thereon. The control system 255 then caused rotation of the wafer to stop and the deposition device 25 was moved to the next wafer over a time period of about thirty seconds to dispense another liquid sample thereon.
  • a predetermined program pursuant to which the wafer was rotated at an acceleration rate of about 2000 rpm/sec until the rotational speed reached about 3000 rpm (e.g., about 1.5 seconds), and rotation then continued at a speed of 3000 r
  • FIG. 21 illustrates yet another embodiment of apparatus 321 of the present invention which is similar to the apparatus 221 of Fig. 11 but with a heating system, generally designated 351 , positioned above the substrates for heating the substrates and the liquid samples deposited thereon.
  • the heating system 351 of the illustrated embodiment comprises an infrared heater 353 positioned a distance of about 1 mm up to about 100 mm above the substrate.
  • the heater 353 is preferably capable of generating heat at a temperature in the range of about 30°C to about 500°C, more preferably in the range of about 50°C to about 450°C, and most preferably in the range of about 100°C to about 400°C.
  • the apparatus 221 , 321 described above can be used for forming thin films in the same manner previously described, the only differences being that liquid samples are deposited on more than one substrate 223, and more than one substrate is moved during overlapping durations of time. Liquid samples of the same or different composition and/or volume may be deposited on different substrates 223 and at the same or different locations on different substrates.
  • different numbers of samples may be placed on different substrates 223 (e.g., one sample on one substrate and more than one sample on other substrates), and the conditions under which the films are formed may be varied by varying the amplitude and/or frequency of movement(s), the duration of movement, etc. This is facilitated in certain embodiments by the use of the control system 255 described above. If a heater 353 or cooling device is used, the temperatures of the substrates 223 may also be controlled.
  • the substrates 23, 223 are removed from their respective holders. It is contemplated that for some films, such as dielectric films, the substrates 23, 223 may be subjected to an annealing process in which the substrates are heated, such as to about 400°C, to promote decomposition of any organic material remaining in the film. However, annealing of the substrates 23, 223 may be omitted without departing from the scope of the invention.
  • a preferred technique for determining the hardness and modulus of elasticity of each film is commonly referred to as nanoindentation, wherein a diamond tip (not shown) is driven down into the film and the resistance of the film to indentation by the diamond tip is measured.
  • One preferred device (not shown) for carrying out such a screening is available from Hysitron Inc. of Minneapolis, Minnesota and designated as a triboindentor nanomechanical test system.
  • the films formed on the substrate 23, 223 are each preferably sized to have a width and length (or diameter) of at least about 50 nm to about 100 nm. Electrical properties of each film, such as the capacitance and the dielectric constant (k) thereof, may also be determined.
  • a device available from Solid State Measurements Inc. of Pittsburgh, Pennsylvania, U.S.A. under the model designation SSM 495 measures the capacitance of a film and, based on the thickness of the film (e.g., as determined by using the techniques described previously), determines the dielectric constant thereof.
  • the films formed on the substrate 23, 223 are each preferably sized to have a surface area of at least about 3 mm 2 .
  • the films may also be screened for various optical properties such as the refractive index (n) and the extinction coefficient, which is a measurement of the amount of light absorbed by the film.
  • One device (not shown) for determining these optical properties is available from n&k Technology of Santa Clara, California, U.S.A. under the model designation n&k Analyzer 1500.
  • the above-described methods and apparatus may be employed as part of a larger system, or workflow, for preparing and identifying thin films which have desirable properties, including for example, mechanical, electrical, thermal, morphological, optical, magnetic, chemical, etc., as further described herein. More specifically, the methods and apparatus of the present invention may be employed as part of a combinatorial method of research, as well as part of an apparatus or a system designed for carrying out such a method of research, wherein a library of materials or compounds or components (some times referred to herein as the parent library), from which samples are taken to form thin films that are subsequently examined for a particular film property of interest, are prepared. Each member of the parent library generally differs in some way from the others, for example due to chemical composition or process history; that is, the parent library may have chemical or process diversity, as further described herein.
  • processing conditions that may be varied or controlled include, for example, (i) in the case of compound or material preparation, varying amounts (e.g., volume, moles or mass) and ratios of starting components, time for reaction, reaction temperature, reaction pressure, rate of starting component addition to the reaction, timing of starting component addition to the reaction, residence time or the time the components are allowed to remain in contact to react, or alternatively the product removal rate, reaction atmosphere, mixing or stir rate, duration of aging or storage, and (ii) in the case of film deposition or preparation, the conditions under which samples are placed on the substrate surface and spread to form a thin layer (e.g., the amount of material or compound deposited on the substrate surface, the force applied to or the manner by which the sample is spread over the surface, the concentration or viscosity of the sample), the conditions under which the sample is then cured to form a film, etc., as well as other conditions that are well recognized by those of ordinary skill in the art.
  • varying amounts e.g., volume, moles or mass
  • each daughter library may be considered to be a replica of the parent library, but each member of the daughter library would be smaller than the corresponding parent member in terms of either volume or moles or mass.
  • each daughter library may also possess chemical or process diversity.
  • members of the libraries will in some instances be a liquid or fluid, in other instances the members may be, for example, in solid, suspension or dispersion form. In such cases, however, samples which are to be used to prepare thin films for testing are dissolved in a suitable solvent before being further processed in accordance with the present invention.
  • such a combinatorial method provides for different screening stages, such as a primary test or measurement to eliminate some members from a library from undergoing further processing or on to a secondary test.
  • films may be subjected to a series of tests, the series essentially encompassing any test that may be of potential interest, such that a large amount of data can be collected at one time.
  • the resulting product library of thin films is tested or measured in some way, the data being collected in a database for further processing and evaluation; that is, the data collected upon testing of a film itself is collected and correlated with other data in the database (including for example the conditions under which the film, or the material from which it was derived, was formed or prepared, as well as the composition thereof), in order to identify a film having the desired properties.
  • potential candidate films i.e., films having properties falling with parameters previously set
  • more of the material from which the identified film was formed may be prepared as needed (e.g., 5X, 10X, etc.
  • a larger or scale-up film prepared e.g., a single film is formed on the surface of a given substrate, rather than multiple films, or alternative a film is formed on the surface of a larger substrate, using for example common spin- coating techniques known in the art.
  • the resulting scale-up film is then further tested to evaluate its properties against (i) the results from the identified film, to determine if anything changed as a result of the scale-up, and/or (ii) pre- determined parameters, in order to identify a film having the desired properties on the desired scale. As such, several iterations of the described process may in some cases be performed. Furthermore, such results may be used to determine when additional, new parent libraries of diverse compounds or materials are needed for further study (e.g., when no film falls within the pre-determined criteria).
  • this combinatorial method accordingly enables the generation and collection of a large amount of data that may be used for screening for various purposes. More specifically, this method enables data to be collected by means of, for example, simply testing or measuring a given material's various properties for collection, or conducting a more sophisticated screening process, wherein a given material is measured for a particular property or group of properties of interest, which are then compared to some predetermined criteria to determine or evaluate that material's potential use for a given purpose (i.e., the material is measured to determine if it passes or fails as compared to a particular figure of merit).
  • a parent library is a library that comprises members possessing chemical and/or process diversity, which are to be formed into thin films using the methods and/or apparatus described herein, which are then screened for a property of interest.
  • chemical diversity generally refers to a library having members that vary in terms of atoms or molecules
  • process diversity generally refers to a library having members that may have begun with the same atoms or molecules, but which have subsequently been subjected to different processing conditions and are different as a results thereof.
  • the members of this library may essentially be anything that can be formed into a thin layer on a substrate surface and sufficiently screened or tested or measure for a property of interest, as described herein. More specifically, as described herein, in at least some embodiments, the thin films of the present invention are to be formed by means of depositing a sample or aliquot of the material or compound on the surface of a substrate, in liquid form, and then subjecting the sample, either directly (e.g., by subjecting to a stream of air) or indirectly (e.g., by movement of the substrate itself), to some spreading force to cause the sample to disperse or spread over the substrate surface.
  • the liquid from which each film is formed may be substantially any liquid solution, dispersion or suspension from which a film remains upon evaporation of the solvent.
  • the liquid may be a material from which, upon evaporation, decomposition or otherwise reaction, a film is formed of silicon dioxide, polyimides or other organic polymers (e.g., non-biological organic polymers), ceramic materials, composite materials (e.g., inorganic composites, organic composites and combinations), photoresists, sol-gel solutions including polymeric metal (organic) oxoalkoxides, other metallo-organic compounds, polymer based light-emitting materials including plastic, solutions and suspensions of ferroelectric materials, and optical coatings.
  • organic polymers e.g., non-biological organic polymers
  • ceramic materials e.g., composite materials (e.g., inorganic composites, organic composites and combinations), photoresists, sol-gel solutions including polymeric metal (organic) oxoalkoxides
  • Such materials or compounds may be prepared by techniques common in the art, including for example, solution-based synthesis techniques, photochemical techniques, polymerization techniques, template-directed synthesis techniques, epitaxial growth techniques, by the sol-gel process, by thermal, infrared or microwave heating, by calcination, sintering or annealing, by hydrothermal methods, by flux methods, by crystallization through vaporization of solvent, etc.
  • solution-based synthesis techniques photochemical techniques, polymerization techniques, template-directed synthesis techniques, epitaxial growth techniques, by the sol-gel process, by thermal, infrared or microwave heating, by calcination, sintering or annealing, by hydrothermal methods, by flux methods, by crystallization through vaporization of solvent, etc.
  • the material or compound may be such that it forms a film of a sufficient surface area and uniform thickness, such that it can be accurately screened by the appropriate technique.
  • the material or compound is preferably also capable of forming a sample that will yield such a film.
  • the thickness of the films formed on the substrate surface is generally a function of various properties of the liquid (or other sample form) from which the film is formed, such as the viscosity, the wettability (e.g., how well the liquid coats the substrate surface) and the volatility (e.g., the vapor pressure) of the solution or dispersing medium, and the amount of spreading force to which the liquid samples are subjected, as will be described elsewhere herein.
  • the more viscous the liquid sample the thicker the resulting film will be for a given spreading force.
  • the spreading forces e.g., stress magnitudes, strain rates, frequencies, amplitudes and the like
  • the spreading forces can be varied to obtain a desired film thickness.
  • the viscosity of the liquid sample in at least some embodiments, is typically in the range of about 1 x 10 "4 to about 1 x 10 4 Pa-sec, preferable in the range of about 5 x 10 "4 to about 1 x 10 3 Pa-sec, more preferably in the range of about 1 x 10 "3 to about 1 x 10 2 Pa-sec, and still more preferably in the range of about 1 x 10 "2 to about 1 x 10 1 Pa-sec
  • materials or compounds which are designed to form low dielectric films such as those described in European Patent Application No. EP 1 142 832 A1 , may be used. More specifically, in one instance this combinatorial method may be employed with low dielectric materials, thin films formed therefrom, and the methods for making same.
  • two measured attributes of interest of a low dielectric material may be correlated into one figure of merit, the normalized wall elastic modulus (E 0 '), that can be used to identify and develop improved low dielectric materials (i.e., materials having low dielectric constants yet high enough elastic modulus to tolerate subsequent processing steps, such as etching and CMP processes).
  • E 0 ' normalized wall elastic modulus
  • materials with substantially identical normalized wall elastic modulus values belong to a family of materials whose dielectric constant and elastic modulus can be adjusted by varying the porosity; that is, by determining the normalized wall elastic modulus of a dielectric material, it may be possible to tune the dielectric constant and elastic modulus of the film of the invention by varying the pore size and distribution of the pores in the film.
  • the target dielectric constant can be obtained by varying the porosity.
  • normalized wall elastic modulus refers to the wall elastic modulus of a material that is normalized to a wall with a dielectric constant of 4.2, which is the dielectric constant of a Si0 2 dense oxide material.
  • the E 0 ' of the material is calculated using Maxwell's relationship for mixed dielectrics applied to porous materials, the measured value for dielectric constant (K), a wall ⁇ Sl02 of 4.2, Day's 2-d circular hole model for elastic modulus extended to 3-d cylindrical pores with the modulus measured perpendicular to the pore axes, and the measured value for E.
  • the low dielectric materials may have a dielectric constant of about 3.7 or less, about 2.7 or less, or less than about 1.95. Such materials may also have a normalized wall elastic modulus (E 0 '), derived in part from the dielectric constant of the material, of about 15 GPa or greater, about 20 GPa or greater, or greater than about 26 GPa. Further, in some instance, the materials may have alkali impurity levels less than about 500 ppm.
  • E 0 ' normalized wall elastic modulus
  • the materials may have a dielectric constant of about 2.0 or less, a normalized wall elastic modulus that ranges from between about 5 GPa to about 15 GPa, and have a metal impurity level of less than about 500 ppm (e.g., less than about 250 ppm, 1 ppm, 500 ppb, 100 ppb, 10 ppb).
  • the material may have (i) a dielectric constant of about 4 or less, a normalized wall elastic modulus (E 0 ') of about 15 GPa or greater, and a metal impurity level of about 500 ppm or less; (ii) a dielectric constant of less than about 1.95 and a normalized wall elastic modulus (E 0 ') of greater than about 26 GPa; or, (iii) a dielectric constant of less than about 2.0, a normalized wall elastic modulus (E 0 ') that ranges from between about 5 GPa to about 15 GPa, and a metal impurity level of about 500 ppm or less.
  • the film may optionally be porous, may optionally not exhibit a diffraction peak, and/or may optionally comprise silica-carbon bonds, all as further described herein.
  • These low dielectric materials may comprise silica.
  • the term "silica,” as used herein, is a material that has silicon (Si) and oxygen (O) atoms, and possibly additional substituents such as, but not limited to: other elements such as H, C, B, P, or halide atoms; alkyl groups; or aryl groups.
  • the material may further comprise silicon-carbon bonds having a total number of Si-C bonds to the total number of Si atoms ranging from between about 20 to about 80, or from between about 40 to about 60 mole percent.
  • the parent library may be created by combinatorial chemistry methods generally known in the art (see, for purposes of illustration, methods for preparing libraries described in co-pending U.S. Patent Application No. 08/327,513 entitled “The Combinatorial Synthesis of Novel Materials," published as WO 96/11878), wherein for example reagents or starting components are added to an array or matrix of wells of a common receptacle or substrate. It is to be noted, however, that the method of preparing or synthesizing the members of the parent library is not narrowly critical here.
  • one or more of the parent libraries may be stored and retrieved from a storage rack for transfer for further use, such as to a daughtering apparatus or a diluting apparatus or a dissolution apparatus or a film- forming apparatus.
  • a daughtering apparatus or a diluting apparatus or a dissolution apparatus or a film- forming apparatus Such retrieval and transfer to another apparatus, to station wherein the apparatus is located, may be automated using known automation techniques, such as those disclosed in PCT Application No. WO 98/40159.
  • Robotic apparatus is commercially available, for example from Cavro, Tecan, Robbins, Labman, Bohdan or Packard, which are companies that those of skill in the art will recognize.
  • the parent library may additionally include standards, blanks, controls or other members that are present for other reasons.
  • the parent library may have two or more members which are identical as a redundancy option, or when reaction conditions or film- forming conditions (rather than material or compound composition) are to be combinatorialized.
  • the members of the parent library may be in the form of a solid, suspension, dispersion or solution for storage purposes; however, when in the form of a solid, dispersion or suspension, the members are typically dissolved in a suitable solvent before being used to form thin films.
  • the parent library or array may consist of, for example, about 10, 100, 10 3 ,
  • the density of the regions wherein each compound or material is contained may be greater than about 0.04 regions/cm 2 , greater than about 0.1 regions/cm 2 , greater than about 1 region/cm 2 , greater than about 10 regions/cm 2 , or greater than about 100 regions/cm 2 .
  • the density of regions per unit area may be greater than about 1 ,000 regions/cm 2 , about 10,000 regions/cm 2 , about 100,000 regions/cm 2 , about 1 ,000,000 regions/cm 2 , or even about 10,000,000 regions/cm 2 .
  • the product library is formed by removing a sample or an aliquot of one or more members of the parent library (or daughter library) and depositing that sample on a substrate surface to form a thin film using the methods and/or apparatus described here.
  • the product library therefore, obtains its diversity either by chemical diversity of the starting components (e.g., the composition of the materials from which the thin films are formed), or by process diversity introduced during preparation of the composition or materials and/or the thin films, or both.
  • screening generally refers to testing or measuring a library for one or more properties or compounds or. materials; that is, “screening” generally refers to measuring one or more properties of interest of a library member (e.g., a parent or daughter array or library compound or material, or a product array or library film), in order to ultimately determine if that member meets a pre-determined criterion.
  • a library member e.g., a parent or daughter array or library compound or material, or a product array or library film
  • a compound or material or film may be (i) measured by a given technique, the data from this measurement being collected and stored, and optionally being reviewed at some later point in time for purposes of comparison with a particular criterion, or (ii) measured by a given technique which includes with it the step of comparing the data of this measurement with a particular criterion, and wherein only the data for the compound or material which meets this criterion is stored for future consideration.
  • multiple parent arrays or libraries of compounds or materials are preferably prepared and used to generate or form multiple product libraries, which are then subjected to multiple tests or measurements.
  • a large database can be generated which can be used in many different ways to collect useful information (e.g., to identify compounds or films for further study or use). This approach is described further herein below.
  • IMPURITIES The properties listed in Table I can be tested for or measured using conventional methods and devices known to and used by those of skill in the art.
  • Scanning systems which can be used to measure for the properties set forth in Table I include, but are not limited to, the following: scanning Raman spectroscopy; scanning NMR spectroscopy; scanning probe spectroscopy including, for example, surface potentiometry, tunnelling current, atomic force, acoustic microscopy, shearing-stress microscopy, ultra fast photo excitation, electrostatic force microscope, tunneling induced photo emission microscope, magnetic force microscope, microwave field-induced surface harmonic generation microscope, nonlinear alternating-current tunneling microscopy, near-field scanning optical microscopy, inelastic electron tunneling spectrometer, etc.; optical microscopy in different wavelengths; scanning optical ellipsometry (for measuring dielectric constant and multilayer film thickness); scanning Eddy- current microscope; electron (diffraction) microscope, etc.
  • scanning Raman spectroscopy scanning NMR
  • Optical inspection in order to determine for example the refractive index (n) and thickness of the film, as well as the extinction coefficient (which is a measurement of the amount of light absorbed by the film).
  • the thickness of the film is determined using a stylus in physical contact with the film.
  • One machine for making such determinations the film thickness in such a manner is available from KLA/Tencor Corp. of San Jose, California, U.S.A. under the model designation P-15.
  • an n&k Analyzer 1500/1512 commercially available from n&k Technology (Santa Clara, CA), can be used, which collects optical spectra and then, using "goodness of fit,” compares the spectra to models to extract the refractive index and thickness of each spectra collected.
  • Electrical inspection in order to determine for example the dielectric constant (by measuring the capacitance and thickness).
  • One device for determining dielectric constant is commercially available from Solid State Measurements Inc. (Pittsburgh, PA), under the model designation SSM 495. This device measures the capacitance of a film and, based on the thickness of the film (e.g., as determined by using the techniques described previously), determines the dielectric constant thereof.
  • the films formed on the substrate are each preferably sized to have a surface area of at least about 3 mm 2 .
  • the films formed on the substrate are each preferably sized to have a width and length (or diameter) of at least about 50 nm to about 100 nm.
  • the thickness of the films may range from about 50 A to about 100 ⁇ m, or preferably from about 1 ,000 A to about 10,000 A.
  • a portion of the surface area of each film formed on the substrate preferably has a substantially uniform thickness to facilitate more accurate screening of the film, this portion having a thickness which is uniform to within a variation of less than about 20%, 10%, 5%, 3%, 2% or even 1 %, with the most preferred being substantially no variation (the thickness uniformity ranging, for example, from about 0% to about 20%, preferably from about 0% to about 10%, more preferably from about 0% to about 5%, and most preferably from about 0% to about 3%).
  • the size (e.g., surface area) of a region within each film formed on the substrate surface is preferably at least about equal to the minimum size required by the measurement method used to characterize the film, and is more preferably up to about three times larger than this minimum size.
  • Dielectric films are also preferably mesoporous.
  • the term "mesoporous”, as used herein, describes pore sizes that range from about 10 A to about 500 A, preferably from about 20 A to about 100 A, and most preferably from about 20 A to about 50 A. It is also preferred that these film have pores of uniform size, and that the pores are homogeneously distributed throughout the film.
  • Such films also preferably have a porosity of about 50% to about 80%, more preferably about 55% to about 75%. The porosity of the films may be closed or open pore. Furthermore, in certain instances, the diffraction pattern of the film does not exhibit diffraction peaks.
  • Dielectric materials also preferably have mechanical properties that allow them, when formed into films, to resist cracking and enable them to be chemically/mechanically planarized. Further, these films preferably exhibit low shrinkage. Finally, these films preferably exhibit a modulus of elasticity of between 1.4 and 10 GPa, and more preferably between 2 and 6 GPa; a hardness value between 0.2 and 2.0 GPa, and more preferably between 0.4 and 1.2 GPa; and, a refractive index determined at 633 nm of between 1.1 and 1.5.
  • Suitable applications for such dielectric films include, for example: (i) interlayer insulating films for semiconductor devices, such as LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, and D-RDRAMs; (ii) protective films, such as surface coat films for semiconductor devices; (iii) interlayer insulating films for multilayered printed circuit boards; and, (iv) protective or insulating films for liquid- crystal display devices. Further applications include capping layers, hard mask, or etch stops.
  • System 1000 includes a parent library 1002, a film-forming apparatus, optionally located as a film-forming station, 1004, a testing or measuring apparatus 1006 and a data collection apparatus, or database, 1008, and optionally a daughtering apparatus 1010 (to create one or more daughter libraries) and/or a filtering apparatus 1012.
  • the system may include storage apparatus 1014, wherein stored may be one or more of (i) the reactants or starting components 1016 used to prepare the members of the parent library, (ii) materials or compounds ready for use as members of a parent library, and/or (iii) finished parent libraries ready for use.
  • a combining/reaction apparatus 1018 may be used.
  • members may be proceed directly to the film-forming apparatus 1004, or they may (i) pass through a combining/dissolution apparatus 1020, where they are mixed with other components (e.g., a solvent, which may or may not be needed to dissolve the member), (ii) a filtering apparatus 1012, or (iii) a daughtering apparatus 1010 (either directly or after passing through the filtering station).
  • An automated robotic system represented by arrows 1022, may be used to move libraries from one apparatus or station to another.
  • a given apparatus may serve more than one function; for example, reaction may occur at or within the combining apparatus, once the starting components are combined.
  • each function may occur in a separate apparatus, at a separate location within the system.
  • each apparatus may be individually located at a separate station within the system, or alternatively two or more apparatuses may be located at the same station (e.g., combining and reaction apparatus located at a single combining/reaction station).
  • station refers to a location within the system whereat one or more functions are performed. The functions may be combining the starting components, creating a parent library via a reaction, forming a film from a member of the parent library, testing or measuring the film or a member of the parent library before film formation, or any of the other functions discussed above.
  • starting components or parent compound or material libraries, etc. are inputted into the apparatus (or retrieved from storage) and sent either to a combining/reaction apparatus 1018 or directly to the parent library 1002 (if the compound or material was previous prepared).
  • members may be tested to confirm composition (not shown), and/or filtered and/or daughtered and/or combined/reacted with other components.
  • thin films are formed via the film-forming apparatus 1004, using for example various spin-coating techniques described herein. Finally, the resulting films are measured or tested for one or more properties of interest.
  • a daughter library is created from the parent library at a daughtering apparatus by taking one or more aliquots from one or more members in the parent library, wherein an aliquot is a definite fraction of a whole.
  • This process is referred to as "daughtering."
  • a liquid pipette operated either manually or automatically (e.g., robotically), draws a bit of a member from the parent library and dispenses that aliquot into another container to give a daughter library member.
  • a limited number of members of the parent library may be daughtered or all the members may be daughtered at least once to create one daughter library.
  • a daughter library may be smaller than the parent library in terms of either mass, volume or moles and/or in terms of the number of members.
  • the members of the parent library are maintained in a solid form.
  • known solid handling equipment and methods are used to take the aliquot from the parent library to created the daughter library, which will have members that are also solids. Thereafter, it may be necessary to dissolve the members of the daughter libraries in a solvent.
  • Daughtering is performed in order to provide multiple libraries for multiple reactions of interest or multiple screens without having to recreate the parent library.
  • a testing or measuring station may include a single or multiple apparatuses (such as for a primary/secondary testing approach, or for a multiple testing approach wherein all samples are subject to multiple tests); alternatively, multiple locations (i.e., stations) may be used for the multiple tests.
  • a feed-back loop 1024 takes information from, for example, the combining/reaction apparatus 1018 (when a reaction that includes a test or measurement is used to form a parent library member or to collect compositional information) or the testing apparatus 1006 (via the database 1008).
  • the information from the testing apparatus 1006 may be used at the starting component apparatus, the reaction/combining apparatus 10018 and/or the storage apparatus 1014 for the preparation of new parent libraries, or alternatively for the scale-up of a candidate for further study.
  • a user of the "control" system 1028 may design a set of experiments to create a product library, specify the test of that product library and command the system to perform all the chemistry and testing automatically from chemicals in storage.
  • the robotic apparatus 1022 preferably includes an automated conveyer, robotic arm or other suitable device that is connected to the "control" system 1028 that is programmed to deliver the library receptacle or plate (not shown) to respective stations 1020, 1004, etc.
  • the processor is programmed with the operating parameter using a software interface. Typical operating parameters include the coordinates of each apparatus in the system 1000, as well as both the library storage plate and daughter plates positioning locations at each station. Other data, such as the initial compositions of each library member (e.g., parent) may also be programmed into the system.
  • An optional lid having latches for connecting to the storage may also be provided for storage purposes.
  • the library plate may be stored in a rack prior to transfer to the next apparatus, such as a reaction or combining apparatus or a daughtering apparatus.
  • Such libraries may be retrieved from storage either manually or automatically, using known automated robots. Specific robots useful for retrieving such stored libraries include systems such as those marketed by Aurora Biosciences or other known robotic vendors.
  • a parent or daughter library may be stored in a liquid or solid state and retrieved from storage for, in some cases, running in the reaction of interest, daughtering, testing, dissolution and/or combining with other reagents, or combinations thereof.
  • a combining apparatus or a daughtering apparatus includes a daughtering robotic arm that carries a movable probe and a turntable for holding multiple daughter plates while the daughtering step is being performed.
  • the daughtering robotic arm is also movable.
  • the robotic apparatus manipulates the probe using a 3-axis translation system.
  • the probe is movable between vials of reagents or reactants, parent library members, etc. arranged adjacent the parent station, combining/reaction station, etc.
  • the robotic handling apparatus next transports the substrates on which they are formed to a testing or measuring apparatus.
  • This apparatus may be configured to perform multiple tests or measurements using multiple techniques, or alternatively there may be more than one testing or measuring apparatus.
  • such a method and/or system additionally provides for database, or a collection of data, as well as a method of generating and using that database. More specifically, it is to be noted that, this system or method provides:
  • the discovery tool or method is design to generate as much potentially relevant data as possible.
  • all array or library members, and preferably multiple libraries of members are subjected to multiple tests or measurements.
  • a database of information is created, with the data being capable of defining a landscape.
  • This landscape may be graphically viewed in a three-axis graph, with the axes of the graph having data from the database taken from, for example, composition, figure of merit (or property) and preparation method. For example, one may graph porosity versus silica content versus temperature of curing, in order to determine an optimal material or condition for a particular application.
  • speed of measurement and identification of a sample meeting somewhat narrow criteria is the focus, while in the second example throughput may be sacrificed in order to obtain as much data as possible.
  • throughput is in part a function of not only the number of tests performed, but also the types of test performed. Specifically, optical and electrical test methods are more easily automated and, therefore, more easily performed. In contrast, the measurement of mechanical properties is more time consuming, which a reason while mechanical properties are typically measured or tested after optical and/or electrical properties.
  • a parent library 2002 and preferably multiple parent libraries (not shown), of compounds or materials are designed, using for example Library Studio® 2000 software (which is available from Symyx Technologies, Inc. of Santa Clara, CA and which is published, in part, as WO 00/23921 ), and prepared (as described elsewhere herein).
  • Library Studio® 2000 software which is available from Symyx Technologies, Inc. of Santa Clara, CA and which is published, in part, as WO 00/23921
  • one or more daughter libraries 2004 may be prepared from the parent library or libraries.
  • a product library or libraries 2006 of thin films may be formed.
  • All (or substantially all) of the members of these product libraries are then subjected to multiple tests (e.g., 2008, 2010, 2012), thus generating data sets for each test of data elements for each sample.
  • All of the data from these tests is collected in a database 2022 (e.g., an electronic database), and then optionally correlated with a given sample's process history and/or composition (e.g., reagents and process conditions used to prepare the parent compound or material, as well process conditions used to prepare the film, etc.).
  • the database may correlate one data set to one or more different data sets, or data elements within different data sets.
  • an initial filter 2014 may be used to check the goodness of f : iit of the optical spectra; for those films meeting the set criteria (e.g., goodness of fit of at least about 9850), the thickness and capacitance are used to calculate the dielectric constant for the sample, which is then stored in the database with the rest of the information collected for that sample.
  • the set criteria e.g., goodness of fit of at least about 9850
  • screen means to examine, review or use the collected data to search for or identify a film of interest, such as by comparing a measured property against one or more pre-determined criteria. For those films which are found to meet or satisfy the criteria used to "filter” all of the samples, additional testing may be used. For example, films found to have a certain minimum visual quality and dielectric constant may be screened for mechanical properties 2018 of interest, such as Young's modulus and hardness. This data is stored in the database, and correlated with the rest of the sample data, as well. Finally, these samples may be digitally photographed and stored 2020.
  • thickness may also be determined using a profilometery, ellipsometry or interferometry. Capacitance can be measured by depositing a metal film on top of the sample film of interest and then making electrical measurements.
  • the collected data may be further manipulated 2024 (either manually or by means known in the art) to generate or calculate, for example, additional compositional and/or chemical data sets or data elements for correlation. All of this data may then be screened 2026 to identify candidates having particular desirable properties for scale-up 2028 and additional investigation or study; alternatively, data may be used to determine if additional libraries are needed.
  • this database may be screened at a later date for a different purpose (e.g., to identify samples having a property of interest which is different from the property for which the sample where initially tested/filtered, or alternatively to identify trends in material compositions, process conditions, film-forming conditions, etc.). As a result, the present invention provides a database that is useful for a number of different purposes.
  • the present invention may be used to identify particular compounds, or in this case films, of interest.
  • the present invention is particularly suited for preparing and identifying low dielectric materials, and more specifically identifying films having a thickness of at least about 0.2 microns, a dielectric constant of less than about 2.5, preferably less than about 2.2, and more preferably less than about 2, and a Young's modulus of at least about 2 GPA, and preferably at least about 3 GPa.
  • Such films include a film having a thickness of less than about 0.2 microns, and (i) a dielectric constant of less than about 2.5 and a Young's modulus of at least 3 GPa, (ii) a dielectric constant of less than about 2.2 and a Young's modulus of at least 3 GPa, or (iii) a dielectric constant of less than about 2 and a Young's modulus of at least 2 GPa.
  • Substrate A material having a rigid or semi-rigid surface. In many embodiments, such as in the case of the substrate upon which a thin film is formed, at least one surface of the substrate will be substantially flat. In the case of the compound or material library, it may be desirable to physically separate synthesis regions in the substrate for different materials with, for example, dimples, wells, raised regions, etched trenches, or the like. In some embodiments, the substrate for the compound or material library will itself contains wells, raised regions, etched trenches, etc. which form all or part of the synthesis regions.
  • a predefined region is a localized area on a substrate which is, was, or is intended to be used for formation of a selected material and is otherwise referred to herein in the alternative as a "known" region or simply a "region.”
  • the predefined region may have any convenient shape, e.g., linear, circular, rectangular, elliptical, wedge-shaped, etc.
  • a predefined region and, therefore, the area upon which each distinct material is synthesized or formed is smaller than about 25 cm 2 , preferably less than 10 cm 2 , more preferably less than 5 cm 2 , even more preferably less than 1 cm 2 , still more preferably less than 1 mm 2 , and even more preferably less than 0.5 mm 2 .
  • the regions have an area less than about 10,000 ⁇ m 2 , preferably less than 1 ,000 ⁇ m 2 , more preferably less than 100 ⁇ m 2 , and even more preferably less than 10 ⁇ m 2 .
  • Component is used herein, in some instances, to refer to each of the individual chemical substances that act upon one another to produce a particular material.
  • Solids consisting of atoms or molecules held together by intermolecular forces.
  • Molecular solids include, but are not limited to, extended solids, solid neon, organic compounds, synthetic or organic metals (e.g., tetrathiafulvalene-tetracyanoquinonedimethane (TTF-TCNQ)), liquid crystals (e.g., cyclic siloxanes) and protein crystals.
  • TTF-TCNQ tetrathiafulvalene-tetracyanoquinonedimethane
  • TTF-TCNQ tetrathiafulvalene-tetracyanoquinonedimethane
  • liquid crystals e.g., cyclic siloxanes
  • protein crystals e.g., cyclic siloxanes
  • Inorganic Materials Materials which do not contain carbon as a principal element.
  • the oxides and sulfides of carbon and the metallic carbides are considered inorganic materials.
  • Examples of inorganic compounds which can be synthesized using the methods of the present invention include, but are not restricted to, the following: (a) Inlermetallics (or Intermediate Constituents):
  • Inlermetallic compounds constitute a unique class of metallic materials that form long-range ordered crystal structures below a critical temperature. Such materials form when atoms of two metals combine in certain proportions to form crystals with a different structure from that of either of the two metals (e.g., NiAI, CrBe 2 , CuZn, etc.);
  • Metal Alloys A substance having metallic properties and which is composed of a mixture of two or more chemical elements of which at least one is a metal;
  • Magnetic Alloys An alloy exhibiting ferromagnetism such as silicon iron, but also iron-nickel alloys, which may contain small amounts of any of a number of other elements (e.g., copper, aluminum, chromium, molybdenum, vanadium, etc.), and iron-cobalt alloys;
  • Ceramics Typically, a ceramic is a metal oxide, boride, carbide, nitride, or a mixture of such materials.
  • Ceramics are inorganic, nonmetallic, nonmolecular solids, including both amorphous and crystalline materials. Ceramics are illustrative of materials that can be formed and screened for a particular property using the present invention.
  • Organic Materials Compounds, which generally consist of carbon and hydrogen, with or without oxygen, nitrogen or other elements, except those in which carbon does not play a critical role (e.g., carbonate salts). Examples of organic materials which can be synthesized using the methods of the present invention include, but are not restricted to, the following: (a) Non-biological, organic polymers: Nonmetallic materials consisting of large macromolecules composed of many repeating units.
  • Such materials can be either natural or synthetic, cross-linked or non-crosslinked, and they may be homopolymers, copolymers, or higher-ordered polymers (e.g., terpolymers, etc.).
  • non- biological ⁇ -amino acids and nucleotides are excluded.
  • non- biological, organic polymers exclude those polymers which are synthesized by a linear, stepwise coupling of building blocks.
  • polymers which can be prepared using the methods of the present invention include, but are not limited to, the following: polyethylenes, polypropylenes, other polyolefins, polyacrylates, polymethacrylates, polyacrylamides, polyvinylacetates, polystyrenes, etc.
  • Organometallic Materials A class of compounds of the type R-M, wherein carbon atoms are linked directly with metal atoms (e.g., lead tetraethyl (Pb(C 2 H 5 ) 4 ), sodium phenyl (C 6 H 5 °Na), zinc dimethyl (Zn(CH 3 ) 2 ), etc.).
  • metal atoms e.g., lead tetraethyl (Pb(C 2 H 5 ) 4 ), sodium phenyl (C 6 H 5 °Na), zinc dimethyl (Zn(CH 3 ) 2 ), etc.
  • Composite Materials Any combination of two materials differing in form or composition on a macroscale. The constituents of composite materials retain their identities, i.e., they do not dissolve or merge completely into one another although they act in concert. Such composite materials may be inorganic, organic or a combination thereof. Included with this definition are, for example, doped materials, dispersed metal catalysts and other heterogeneous solids.
  • “Silica source:” as used herein, is a compound having silicon (Si) and oxygen (O), and possibly additional substituents such as, but not limited to, heteroatoms such as H, B, P, or halide atoms; alkyl groups; or aryl groups.
  • “Alkyl:” as used herein, includes straight chain, branched, or cyclic alkyl groups, preferably containing from 1 to 24 carbon atoms, or more preferably from 1 to 12 carbon atoms. This term applies also to alkyl moieties contained in other groups such as haloalkyl, alkaryl, or aralkyl.
  • the term “alkyl” further applies to alkyl moieties that are substituted.
  • “Aryl:” as used herein, typically refers to six to twelve member carbon rings having aromatic character.
  • aryl also applies to aryl moieties that are substituted.
  • the following acronyms are used in the present application:
  • TSE-POSS trisilanolethyl-POSS
  • TEOS 22.5 g
  • MTES 22.5 g
  • PGPE propylene glycol propyl ether
  • Purified Triton X-114 9.7 g was then added to the solvent/silicate mixture and the mixture agitated to produce a clear solution.
  • 1 g of 2.4 wt% TMAH was added to 24 g 0.1 M HNOg and mixed thoroughly.
  • the resulting HN0 3 /TMAH solution was added to the silicate solution and mixed until a clear solution was obtained.
  • the solution was aged for several hours (a minimum 1 hour).
  • the films were optically screened, yielding an average refractive index of 1.232 and a thickness of 10,100 angstroms.
  • the dielectric constant was then measured, yielding an average value of 2.43.
  • the Young's modulus measurements on the films had an average value of 3.1 GPa.
  • the films are generally thicker than those prepared using conventional spin-coating techniques, but the properties of interest (e.g., the dielectric constant and modulus) were equivalent to those prepared conventionally.
  • the properties of interest e.g., the dielectric constant and modulus
  • a Cavro robot was used to aspirate the components and dispense them into a 96-well plate.
  • the components were dispensed with the following order of addition: TEOS, MTES, Triton X-114PGPE solution (mixed 1 :4 v/v), PGPE, water, 0.1 M HN03, and 0.262N TMAH.
  • TEOS Triton X-114PGPE solution
  • PGPE Triton X-114
  • water 0.1 M HN03
  • 0.262N TMAH TMAH
  • the ratio of the different components was identical to that of Example 1 , but the total solution volume is only about 0.5 ml, as opposed to the 400 ml prepared in Example 5.
  • the 96-well plate was then capped and shaken to allow appropriate mixing of the components.
  • the plate is then aged overnight (8 hrs).
  • the robot was then used to aspirate a 0.004 ml sample from the 96-well plate and dispense it on a low resistivity silicon wafer that was situated on a vertical shaker.
  • Several samples (25) were dispensed onto the wafer surface (about 125 mm in diameter) in a generally square pattern (e.g., a matrix of five rows with each row containing five samples), with the spacing between adjacent samples being about 17.5 mm.
  • Dispensing of the liquid samples on the wafer occurred over a period of about 12 minutes, and the substrate was moved on its oscillatory path for a total duration of about 15 minutes (e.g., about 3 minutes longer than the time at which the last liquid sample is deposited on the substrate), after which movement of the substrate was stopped. Linear reciprocating movement of the wafer caused the liquid samples to spread over the wafer surface to form films thereon.
  • the silicon wafer was then baked as in Example 5.
  • the resulting films were optically screened, yielding an average refractive index of 1.228 and a thickness of 10,400 angstroms.
  • the dielectric constant was then measured, yielding an average value of 2.47.
  • the Young's modulus measurements on the films had an average value of 3.0 GPa. Construction and operation of the screening devices described above are well known in the art and will not be further described herein. Moreover, it is contemplated that other conventional screening devices may be used to screen the films formed on the substrate 23, 223, including devices capable of screening for properties other than those described previously, without departing from the scope of this invention.

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Abstract

La présente invention concerne un procédé et un appareil pour produire un réseau ou une pluralité de films à la surface d'un ou de plusieurs substrats. Des échantillons liquides, une fois déposés à la surface d'un ou de plusieurs substrats, sont soumis à une force de dispersion sans contact, telle qu'induite par le déplacement du/des substrat(s), suffisante pour disperser les échantillons sur la/les surface(s) afin d'y former des films respectifs. Dans un autre mode de réalisation, les échantillons liquides sont dispersés sur la surface d'un ou de plusieurs substrats au moyen d'un courant de gaz sous pression. Une fois formés, un ou plusieurs des films peuvent être soumis à un processus de criblage afin de déterminer ou de mesurer une propriété de ceux-ci.
PCT/US2003/015952 2002-05-30 2003-05-20 Appareil et procede pour produire des films sur des substrats WO2004073048A2 (fr)

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US8434422B2 (en) 2009-04-20 2013-05-07 Dow Global Technologies Llc Coating apparatus and method

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Publication number Priority date Publication date Assignee Title
WO2007113560A2 (fr) * 2006-04-04 2007-10-11 Imperial Chemical Industries Plc Formation de film et évaluation
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US8434422B2 (en) 2009-04-20 2013-05-07 Dow Global Technologies Llc Coating apparatus and method

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