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WO2008067308A1 - Croissance de films de sulfure de cadmium dans des conditions aqueuses par une approche biomimétique - Google Patents

Croissance de films de sulfure de cadmium dans des conditions aqueuses par une approche biomimétique Download PDF

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Publication number
WO2008067308A1
WO2008067308A1 PCT/US2007/085635 US2007085635W WO2008067308A1 WO 2008067308 A1 WO2008067308 A1 WO 2008067308A1 US 2007085635 W US2007085635 W US 2007085635W WO 2008067308 A1 WO2008067308 A1 WO 2008067308A1
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Prior art keywords
substrate
film
metal
cds
solution
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Laurie B. Gower
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University of Florida
University of Florida Research Foundation Inc
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University of Florida
University of Florida Research Foundation Inc
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating

Definitions

  • biominerals such as calcium carbonates in abalone nacre and hydroxyapatite in bone
  • organic materials insoluble organic matrix and soluble proteins
  • Precursor process which uses process-directing polymer to mimic the function of soluble protein and induce the highly fluidic liquid precursors for biominerals.
  • the general process introduces the anionic poly-amino acids into an aqueous salt solution which is slowly raised in supersaturation.
  • One common method for raising supersaturation is to slowly introduce one of the ionic species, for example using a modified vapor diffusion technique developed by Addadi et al (Addadi, L. et al. Proc. Natl. Acad. Set USA, 1985, 82:4110-4114), in which ammonium carbonate (NH 4 ⁇ CO 3 vapor, produced by decomposition of its powder, diffuses into a solution containing calcium chloride CaCl 2 and the polymeric additive.
  • This multistage process is illustrated by the formula:
  • This PILP process could provide an alternative explanation as to how the unique microstructures in biominerals are formed, and have demonstrated that means of mimicking such processes.
  • Examples of such microstructures, which can be successfully modeled by PILP. include mollusk shell, sea urchin spine, teeth and bone.
  • SAMs Self-assembled monolayers
  • substrates such as silicon, silicon dioxide, silver, copper, or gold.
  • thiol monolayers on gold surfaces has resulted in technologies such as soft lithography.
  • Applications of SAMs include sensor development, corrosion protection and heterogeneous catalysis.
  • SAMs have been used as templates for organic synthesis and layer-by-layer adsorption. Their interaction with cells and proteins is well understood and micro-structured SAMs have been used to manipulate cells.
  • the method of the invention involves templating an amorphous CdS film, or other inorganic film, onto a desired substrate, such as self-assembled monolayers (SAMs) patterned by soft lithography.
  • a desired substrate such as self-assembled monolayers (SAMs) patterned by soft lithography.
  • SAMs self-assembled monolayers
  • the polymeric process-directing agent stabilizes the amorphous phase and alters the amorphous to crystalline transformation, such that patterning of the amorphous precursor provides a means for regulating the location and morphology of thin films.
  • the products of this invention are useful in the construction of electronic devices, such as photovoltaic cells and thin film transistors.
  • Figure 1 is a micrograph showing the upper surface of abalone nacre.
  • Figure 2 is a micrograph showing a CaCO 3 film on a self-assembled monolayer (SAM), produced by the PILP process.
  • SAM self-assembled monolayer
  • Figure 3 is a TEM image of bone.
  • Figure 4 is a micrograph of mineralized bovine tendon produced via the PILP process.
  • Figure 5 shows a drawing of SAM deposited on gold islands previously coated on a silicon wafer.
  • Figures 7A and 7B show optical micrographs of CdS particles produced by mixing of CdCl 2 and Na 2 S solution.
  • Figure 7A without PAA
  • Figure 7B with PAA (Mw: 8000).
  • Figure 8 is a graph showing XRD patterns of CdS particles produced by mixing of CdCl 2 and Na 2 S solution. The concentration of Cd 2+ and S 2" were 5 mM and reaction time was 3 days. Poly-acrylic acid was added into reacting solution and its concentration was lOO ⁇ g/ml.
  • Figure 9 is a micrograph showing that, upon CdS formation via the vapor diffusion method, without PAA, CdCO 3 was formed at the air/solution interface. CdCO ⁇ aggregates were on the unidentified film that formed at the air/solution interface (5mM Cd 2+ ).
  • Figure 10 is a graph showing XRD pattern of film without PAA.
  • Figures HA and HB are micrographs showing that, upon CdS formation via the vapor diffusion method, with PAA added as a process-directing agent, a very thin and continuous film was formed at the air-solution interface (Figure 1 IA), and the edges of the films showed birefringence (Figure HB). Film formation was observed for every solution containing
  • PAA from concentrations of 2, 5, 10 and 20 ⁇ g/ml, and continuous film was formed from solutions containing 5 ⁇ g/ml of PAA and higher.
  • Figure 1 IA 5mM Cd 2+ , 20 ⁇ g/ml of PAA;
  • Figure 1 IB without gypsum plate.
  • Figure 12 is a graph showing the XRD pattern of a film, which shows a very broad peak of CdS around 26.5 degrees, which was occasionally observed from CdS synthesized from chemical bath.
  • Figures 13A-13D show results of CdS formation on SAM (3 days of reaction). Because of the small thickness of the CdS film deposited on the SAM, an accelerating voltage of SEM was reduced to 4kV in order to see an image of the pattern.
  • Figure 13D shows an SEM image of CdS patterns taken by the BSE mode.
  • Figure 13A 5mM Cd 2+ , 20 ⁇ g/ml of PAA
  • Figure 13B 5mM Cd 2+ , 20 ⁇ g/ml of PAA
  • Figure 13C 5mM Cd 2+ , without PAA
  • Figure 13D 5mM Cd 2+ , 20 ⁇ g/ml of PAA.
  • Figures 14A-14C show a micrograph ( Figure 14A) and two graphs showing XRD peaks ( Figures 14B and 14C).
  • Figures 15A-15F are micrographs demonstrating the influence of solution concentration and polymer.
  • Figure 15A 10 mM Cd 2+ , 20 ⁇ g/ml of PAA
  • Figure 15B 10 niM Cd 2+ , 20 ⁇ g/ml of PAA
  • Figure 15C 20 mM Cd 2+ , 20 ⁇ g/ml of PAA
  • Figure 15D 5 mM Cd 2+ , 20 ⁇ g/ml of PAA
  • Figure 15E 5 mM Cd 2+ , 20 ⁇ g/ml of Pasp.
  • Figure 16 shows a schematic diagram of simple reaction apparatus to prevent the evaporation of reacting solution.
  • Figure 17 shows a Polarized optical microscope image of CdS precipitates after 2 days of reaction.
  • Figure 18 shows an X-ray diffraction pattern of CdS precipitate from reaction solution with poly-acrylic acid.
  • Figure 19 shows a polarized optical microscope image (with gypsum wave plate) of SAM printed on gold substrate, which reacted in the reaction solution without poly-acrylic acid for 3 days. Surface was cleaned by sonication with DI water.
  • Figures 2OA and 2OB show polarized optical microscope images of SAM printed on gold substrate (Figure 2OA: 50 ⁇ m; Figure 2OB: 20 micron), which reacted in the reaction solution with 20 ⁇ g/ml of poly-acrylic acid for 3 days. Surface was cleaned by sonication with DI water.
  • Figures 21A and 21B show scanning electron microscope image (Figure 21A) of
  • Figure 22 shows an atomic force microscope image of CdS film deposited on SAM.
  • Figures 23A and 23B show an atomic force microscope image (Figure 23A) of CdS film on SAM (same region as in Figure 22), and line profile of film (Figure 23B). Line scanning was performed along white line in Figure 23A, and its results are shown in Figure 23B. The film is about 20 run thick.
  • PILP biomimetic approach
  • SAMs self-assembled monolayers
  • process-directing agents such as anionic poly-amino acids, which generate a highly hydrated amorphous precursor, called the polymer-induced-liquid- precursor (PILP) phase
  • PILP polymer-induced-liquid- precursor
  • the present invention provides a method for depositing a film (e.g., a semiconductor film or ceramic film) on a substrate, comprising: providing a substrate (template); contacting the substrate with a metal ion-containing solution (e.g., Cd 2+ ion- containing solution); adding a source of Group Via element, such as sulfur ions, to the substrate (e.g., via vapor diffusion); adding an anionic polymer (e.g., poly-acrylic acid, poly- aspartic acid, etc.) as a process-directing agent; and allowing a film to form on the substrate.
  • a metal ion-containing solution e.g., Cd 2+ ion- containing solution
  • a source of Group Via element such as sulfur ions
  • the films of the invention can be formed on or applied to a substrate, e.g., as a coating or coatings.
  • the substrate can be composed of any of a variety of materials, such as metal, polymer, and/or ceramic materials. Suitable substrates include but are not limited to glass, fused silica, spin-coated polyimide, polycarbonate, polyester, and silicon wafers.
  • substrates e.g., semiconductor wafers
  • photosensitive resist layers formed on substrates, e.g., semiconductor wafers
  • resolution enhancement techniques such as alternating or attenuated phase shift masks, etc., are employed in semiconductor manufacturing.
  • the substrate is a self-assembled monolayer (SAM) patterned by soft lithography.
  • SAM self-assembled monolayer
  • the films may be easily patterned on a surface using standard photolithographic and soft lithographic techniques, enabling multiple fields containing different molecular assemblies to be deposited. InkJet printing and automated (robotic) techniques that can precisely deposit small spots of material on a substrate may also be exploited to pattern the surface.
  • any substrate including all classes of materials, e.g., metals, ceramics, glasses, non-crystalline materials, semiconductors, polymers and composites, may be used or adapted for use with the invention.
  • Substrates may also be combined; for example, a substrate of one material may be coated or patterned with a second material.
  • Such coatings may be desirable to provide a specifically tailored set of bulk and surface properties for the substrate. It is not necessary to coat the entire substrate with the second material.
  • the second material may be deposited according to a periodic or other pattern. For example, an electrical circuit may be deposited on the material.
  • the substrates may also be pretreated before deposition of the film.
  • a range of methods are known in the art that can be used to charge, oxidize, or otherwise modify the composition of a surface if desired, including but not limited to plasma processing, corona processing, flame processing, and chemical processing, e.g., etching, micro-contact printing, and chemical modification.
  • Optical methods such as UV or other high energy electromagnetic radiation or electron beams, may also be employed.
  • the substrate may include an anchor group that facilitates molecular self assembly.
  • Anchor groups form chemical bonds with functional groups on the substrate surface to form a self assembled monolayer (SAM).
  • SAMs having different anchor groups such as silane and thiol may be deposited on a wide variety of substrates, as described in U.S. Patent No. 5,512,131 (Kumar et al).
  • SAMs may be deposited from both the solution and the gas phases onto the substrate.
  • various soft lithography techniques ⁇ e.g. , microcontact printing, microtransfer molding, micromolding in capillaries, replica molding, and micro fluidics, described in Xia, et al, Soft Lithography, Angew. Chem., 1998, 37: 550-575, which is incorporated herein by reference in its entirety), may also be used.
  • Suitable metal salts include but are not limited to water-soluble formate, acetate, sulfate and chloride salts of Cd, Hg, Ag, Mn, Bi, Sb, As Sn, In, Pb, Cu, Co, Ni, Mo, Fe, and Cr. Cadmium is a preferred metal. Thin films of cadmium sulfide (CdS) have major applications in optoelectronic devices.
  • CdS cadmium sulfide
  • Suitable Group Via elements include O, S and Se. Suitable sources of these elements include water (for making metal oxides); thiourea, thioacetamide and Na 2 S 2 O 3 (for making metal sulfides); and selenourea, dimethylselenourea and Na 2 Se 2 O 3 (for making metal selenides). For example, S 2" can be released from thioacetamide.
  • anionic polymers e.g., anionic poly-amino acids
  • PAA polyacrylic acid
  • PMA polymethacrylates
  • sulfonated polymers phosphorylated peptides and polymers, sulfated and/or carboxylated glycoproteins, polyaspartic acid, polyglutamic acid, phosphonates, polyvinyl phosphonates or copolymers thereof
  • a range of polymer molecular weights can be suitable if the other variables of the crystallizing conditions are appropriately modified to generate the PILP phase.
  • a noble metal may be utilized in the deposition method, as described in the Examples.
  • Useful noble metals include, for example, gold, platinum, palladium, silver, nickel, and copper.
  • reaction vessel or vessels utilized for producing the films of the present invention are not critical. Any vessel or substrate capable of holding or supporting the PILP and/or substrate so as to allow the reaction to take place can be used. It should be understood that, unless expressly indicated to the contrary, the terms “adding”, “contacting”, “mixing”, “reacting”, “combining” and grammatical variations thereof, are used interchangeable to refer to the mixture of reactants of the process of the present invention (e.g., anionic poly-amino acids, Cd 2+ ion-containing solution, and so forth), and the reciprocal mixture of those reactants, one with the other (i.e., vice-versa).
  • reactants of the process of the present invention e.g., anionic poly-amino acids, Cd 2+ ion-containing solution, and so forth
  • a composition comprising a hydrated amorphous phase in a metal ion solution is also provided herein.
  • the hydrated amorphous phase comprises metal salts selected from water-soluble formate, acetate, sulfate or chloride salts of Cd, Zn, Hg, Ag, Mn, Bi, Sb, As Sn, In, Pb, Cu, Co, Ni, Mo, Fe, Cr, or combinations thereof, one or more Group Via element and an anionic polymer.
  • the anionic polymer sequesters the metal salts and one or more Group Via element from the metal ion solution.
  • Certain aspects of the invention provide metal salts selected from water-soluble formate, acetate, nitrate, sulfate or chloride salts of Cd.
  • Various other aspect of the invention provide Group Via elements selected from O, S or Se, Te or combinations thereof and anionic polymer selected from polyacrylic acid (PAA), polymethacrylates (PMA), sulfonated polymers, phosphorylated peptides and polymers, sulfated and/or carboxylated glycoproteins, polyaspartic acid, polyglutamic acid, phosphonates, polyvinyl phosphonates or copolymers of these materials
  • a film includes more than one such film, and the like.
  • anionic poly-amino acid includes more than one such “poly-amino acid”.
  • Cd 2+ ion includes more than one such ion, and so forth.
  • SAM templates were prepared by: a. Microcontact printing SAM on gold using soft-lithography
  • Templates were placed in the solution containing Cd 2+ ion, thiourea and triethanolamine by the following procedure: a. Templates is placed in clean petri-dish with up-side down position; and b. Two stock solutions (A, B) were prepared Solution A: 5mM of cadmium acetate and 5mM of triethanolamine Solution B: 5mM of thiourea c. Appropriate poly-acrylic acid solution (lmg/ml) was added into Petri-dish as a process-directing agent, and the final concentration of poly-acrylic acid was adjusted to 20 ⁇ g/ml; and d. Equal amount of solution A and B is added to Petri-dish containing template and poly-acrylic acid; e.
  • Petri-dish was sealed by parafilm without any hole; f. Petri-dish was placed into 65 0 C oven with water reservoir to prevent any undesirable evaporation of the reaction solution (shown in Figure 16) 3.
  • Various concentrations of Cd 2+ and thiourea were used to investigate CdS film deposition at room temperature.
  • Example 1 CdS particle formation via PILP process using thiourea (3 days of reaction)
  • CdS film was examined with Atomic Forces Microscopy (AFM) ( Figure 22). Very smooth film was deposited on the COOH-terminated SAM and no film was observed on the edge (gold region). Small particles were also observed on the CdS film and gold region. It might be nano-particle formed from CdS precursors. A line-scan of the film indicates that the film thickness is around 20 nm ( Figure 23).
  • AFM Atomic Forces Microscopy
  • a smooth CdS film was deposited on the SAM via the PILP process, in which poly-acrylic acid was used to induce CdS liquid precursors and thiourea was used as a sulfur source.
  • the CdS was deposited on the hydrophilic SAM only, and the average thickness is around 20 nm.
  • CdS film was deposited only from 5mM of Cd solution ( Figures 15A-15F). However, uniformity of film and smoothness of surface was poor. Poly-aspartic acid did not show an ability to induce the PILP process under these conditions. Film thickness was measured by Alpha-step 500 (Tencor), and the average thickness of the CdS film was 11.3 nm.
  • CdS films was 11.3 nanometers.
  • the pH range of the system was very acidic, and Pasp did not show the ability of forming CdS precursor via the PILP process at pH range 2-3; however, PAA could be used for process-directing polymer for the PILP process at low pH range.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention concerne un procédé de dépôt d'un film céramique (tel qu'un film semi-conducteur) sur un substrat (matrice) dans des conditions aqueuses, et le produit résultant de ce procédé. Le procédé consiste à déposer un film de CdS amorphe, ou un autre film inorganique, sur un substrat, tel qu'une monocouche autoassemblée (SAM), modelé par lithographie douce. L'agent polymère dirigeant le processus induit une phase amorphe avec des propriétés fluides qui peut coalescer en un film lisse et continu, de telle sorte que le modelage du précurseur amorphe fournit un moyen de réguler l'emplacement et la morphologie de films minces.
PCT/US2007/085635 2006-11-27 2007-11-27 Croissance de films de sulfure de cadmium dans des conditions aqueuses par une approche biomimétique Ceased WO2008067308A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114447151A (zh) * 2022-01-19 2022-05-06 安徽大学 一种用于太阳能电池的硫化镉薄膜的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060072864A (ko) * 2004-12-24 2006-06-28 한국기계연구원 콜로이드 자기조립에 의한 다공성 마스크의 제조방법 및그 용도
US7090868B2 (en) * 2002-09-13 2006-08-15 University Of Florida Materials and methods for drug delivery and uptake

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7090868B2 (en) * 2002-09-13 2006-08-15 University Of Florida Materials and methods for drug delivery and uptake
KR20060072864A (ko) * 2004-12-24 2006-06-28 한국기계연구원 콜로이드 자기조립에 의한 다공성 마스크의 제조방법 및그 용도

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GOWER L.B. ET AL.: "Deposition of calcium carbonate films by a polymer-induced liquid-precursor (PILP) process", JOURNAL OF CRYSTAL GROWTH, vol. 210, 2000, pages 719 - 734, XP004191390, DOI: doi:10.1016/S0022-0248(99)00749-6 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114447151A (zh) * 2022-01-19 2022-05-06 安徽大学 一种用于太阳能电池的硫化镉薄膜的制备方法

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