Classifications

• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
  • C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/40—Oxides
  • C23C16/401—Oxides containing silicon
  • C23C16/402—Silicon dioxide
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/52—Controlling or regulating the coating process
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
  • Y10T428/24521—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness with component conforming to contour of nonplanar surface

Definitions

• the present invention relates to a substrate structure comprising a substrate and a plasma grown layer, the surface of the resulting substrate structure being characterized by interrelated scaling components, the scaling components comprising a roughness exponent ⁇ , a growth exponent ⁇ and a dynamic exponent z.
• the present invention relates to a method for producing a substrate structure comprising providing a substrate in a treatment space, providing a gas mixture in the treatment space, and applying a plasma in the treatment space to deposit a layer of material on a surface of the substrate, wherein the surface of the resulting substrate structure is characterized by interrelated scaling components, the scaling components comprising a roughness exponent ⁇ , a growth exponent ⁇ and a dynamic exponent z.
• Thin films on substrates which are grown using various processes may be characterized by certain characteristic parameters, such as surface roughness CC. Further characteristic parameters are growth exponent ⁇ and dynamic exponent z. These three parameters are in general interrelated as z ⁇ ⁇ / ⁇ .
• the components thus formed may be applied in various applications, such as semiconductor processing, optical coating, plasma etching, patterning, micromachining, polishing, tribology, etc.
• a substrate structure according to the preamble defined above wherein the growth exponent ⁇ has a value of less than 0.2 and the dynamic exponent z has a value of more than 6.
• This characterization of the surface of a substrate structure with a thin film layer was yet unknown.
• the dynamic exponent z has a value of about 9, e.g. 10. This allows to have layers of various thickness, without influencing other characteristic features such as surface roughness. Furthermore, in an even further embodiment, the roughness exponent ⁇ has a value of about 0.9.
• the growth exponent ⁇ has a value of equal to or less than 0.1 in an even further embodiment.
• the value of the growth exponent can even be as small as 0.01, or even 0. This provides a substrate structure with even better properties, where the roughness of its surface is not influenced by a thickness t of the deposited thin layer. This allows the purposeful design of structures over a wide range of thickness of the substrate.
• the substrate is provided with protrusions on its surface having a first height hi, and the layer is grown to a thickness t which is smaller than the first height hi in a further embodiment.
• This may provide for a substrate structure with an 'open' surface, as a small part of the vertical wall of the protrusion remains without the added layer.
• the substrate is provided with protrusions on its surface having a first height hi, and the layer is grown to a thickness t which is larger than the first height hi.
• the layer seals off any possible protrusions on the substrate (such as impurities or particles) and provides a closed surface, which is particularly advantageous when manufacturing barriers.
• the protrusions comprise a pattern. This would e.g. allow to manufacture membranes having a high selectivity.
• a method is provided as described in the preamble above, wherein the growth exponent ⁇ has a value of less than 0.2 and the dynamic exponent z has a value of more than 6.
• the method is further arranged to provide a substrate structure for which the various scaling components CC, ⁇ and z have values in ranges as discussed above relating to various embodiments of the substrate structure.
• the substrate is provided with protrusions on its surface having a first height hi .
• this allows to grow layers on a substrate, wherein the form of the protrusions is accurately preserved.
• the thickness of the layer is adapted to a maximum size of particles possibly present in the treatment space in a further embodiment, to allow formation of a complete thin layer without any openings.
• the plasma is an atmospheric pressure glow discharge plasma which is generated using an AC power supply having a duty cycle of up to 100%.
• AC power supply having a duty cycle of up to 100%.
• the plasma is an atmospheric pressure glow discharge plasma which is generated comprising an oxygen concentration from 6% to 21% in the treatment space.
• the present invention relates to a substrate deposition apparatus comprising a treatment space formed between at least two electrodes, a power supply connected to the at least two electrodes, the power supply being arranged to generate an plasma in the treatment space, a gas supply for providing a gas mixture in the treatment space, wherein the surface deposition apparatus is arranged to implement the method according to any one of the method embodiments as described above.
• Fig. 1 shows a cross sectional view of an exemplary embodiment of a substrate structure according to the present invention
• Fig. 2 shows a schematic diagram of a substrate deposition apparatus according to an embodiment of the present invention
• Fig. 3 shows a graph representing a number of characterizing parameters of a substrate surface
• Fig. 4 shows a graph of measured rms roughness of a number of exemplary embodiments of substrate structures according to the present invention
• Fig. 5 shows a graph of the auto-correlation function of surface heights separated laterally by a vector r;
• Fig. 6a and 6b show cross sectional views of further exemplary embodiments of the substrate structure according to the present invention.
• Fig. 7a shows a graph presenting the height-height correlation function for various embodiments of the substrate structure of the present invention, in which HMDSO has been used as precursor;
• Fig. 7b shows a graph presenting the height-height correlation function for various embodiments of the substrate structure of the present invention, in which TEOS has been used as precursor.
• the present invention embodiments relate to layer deposition processes on a substrate film 6, using an atmospheric pressure glow discharge plasma in a treatment space of a substrate deposition apparatus 10 to deposit a thin film layer 6a on the substrate 6 to obtain a substrate structure 7, as shown in cross section in Fig. 1.
• the substrate structure 7 obtained using this process is characterized by specific surface properties of the substrate structure 7. These specific surface characteristics make the substrate structure 7 very suitable for production of several semi-finished products.
• polymer films may be used as substrate 6, onto which a layer 6a Of SiO 2 may be deposited to obtain substrate structures 7 in the form of foils or films with specific characteristics such as improved water vapor transmission ratio (WVTR) or oxygen transmission ratio (OTR).
• WVTR water vapor transmission ratio
• OTR oxygen transmission ratio
• These semi-finished products may then be used for manufacturing LCD-screens, photovoltaic cells, etc.
• Fig. 2 shows a schematic view of a plasma treatment apparatus 10 in which the substrate structures 7 according to the present invention may be obtained.
• a treatment space 5 which may be a treatment space within an enclosure 1 or a treatment space 5 with an open structure, comprises two opposing electrodes 2, 3.
• a substrate 6, or two substrates 6 can be treated in the treatment space 5, e.g. in the form of flat sheets (stationary treatment, shown in Fig. 2) or in the form of moving webs.
• gas supply device 8 In the treatment space 5, a mixture of gasses is introduced using gas supply device 8, including a reactive gas and a pre-cursor. It was observed that the oxygen as a reactive gas needs to be controlled in the range above 5% (e.g. 6%, 10%, 15%) up to 21% in the treatment space to make the inventive products.
• the gas supply device 8 may be provided with storage, supply and mixing components as known to the skilled person. The purpose is to have the precursor decomposed in the treatment space 5 to a chemical compound or chemical element which is deposited on the substrate 6 as thin layer 6a.
• the electrodes 2, 3 are connected to a plasma control unit 4, which inter alia supplies electrical power to the electrodes 2, 3, i.e. functions as power supply.
• the plasma discharge in the treatment space 5 is controlled by special circuitry to sustain a very uniform plasma discharge at atmospheric pressure, even up to a 100% duty cycle.
• Both electrodes 2, 3 may have the same configuration being flat orientated (as shown in Fig. 2) or both being roll- electrodes. Also different configurations may be applied using roll electrode 2 and a flat or cylinder segment shaped electrode 3 opposing each other.
• a roll-electrode 2, 3 is e.g. implemented as a cylinder shaped electrode, mounted to allow rotation in operation e.g. using a mounting shaft or bearings.
• the roll-electrode 2, 3 may be freely rotating, or may be driven at a certain angular speed, e.g. using well known controller and drive units. Both electrodes 2, 3 can be provided with a dielectric barrier layer, or the substrate 6 can act as dielectric barrier layer.
• a large number of thin films 6a with varying thickness were deposited on a reference polymeric films 6, so-called APS-PEN or PET (Q65FA) under various oxygen concentration in the treatment space 5.
• the thickness was varied by changing the line speed of the moving webs 6.
• the PEN-polymer films 6 were deposited using HMDSO as precursor.
• Similar experiments were conducted using TEOS as a precursor and a PET (Q65FA) polymeric film 6.
• the polymer films 6 were deposited using HMDSO as precursor with 19, 24, 99, 142 and 310 nm thick SiO 2 layers 6a (see Fig. 7a), and similarly, using TEOS as a precursor, and a Q65FA polymeric film 6, on which thin films 6a were deposited in thicknesses of 9, 16, 41 and 54 nm SiO 2 (see Fig. 7b)
• the bare polymer film 6 and the series of SiO 2 films 6a were characterized on surface roughness using an atomic force microscope (AFM).
• the surfaces were characterized on 2 x 2 micron scale to investigate roughness on the submicron level.
• Fig. 3 a schematic drawing of an exemplary surface profile is shown, with related parameters ⁇ (wavelength of surface peaks), ⁇ (lateral correlation length of peaks) and w (interface width).
• the mean height h(t) is defined by: &( ' £) ⁇ h(x,t) >, where x is the lateral dimension as shown in the surface profile of Fig. 3, and t is the thickness of the thin layer 6a.
• barrier substrates may be manufactured in the form of such a substrate structure 7 wherein the barrier function may impose requirements on minimum or maximum thickness.
• substrate structures 7 acting as membranes with a high selectivity may be provided, where also requirements may exist with regard to total thickness.
• the correlations in lateral direction can be characterized by the Auto Correlation Function (ACF), see also chapter 2 'Surface Statistics' in the book by Pelliccione et al. mentioned above.
• the ACF measures the correlation of surface heights separated laterally by a vector r.
• the Auto Correlation Function was determined from the bare polymer surface 6 and the substrate structures 7 having thin layer films 6a of 19 and 140 nm SiO 2 . The result is shown in the plot of Fig. 5.
• the Lateral Correlation Function (LCF) (see also chapter 2 of the book by Pelliccione et al) is defined by the 1/e decrease of the ACF. Corresponding value of x at 1/e is the value ⁇ (lateral correlation length of peaks): R ⁇ ⁇ ⁇ X
• Fig. 6a and 6b depict schematically in cross sectional view two examples of a substrate structure 7 with a thin film 6a deposited as described above.
• the substrate 6 is provided with a peak 11 extending a height hi above the surface of the substrate 6.
• the dynamic factor z is high (in the order of magnitude of 10, as shown above), and a thin layer 6a is grown on the surface of the substrate 6, the shape of the peak 11 is maintained almost independent on the thickness t of the layer 6a.
• the surface of the substrate 6 is provided with a peak 11 in the form of a rectangular protrusion with a width 1 (as shown in the cross sectional view of Fig. 6a) and a thin layer 6a is deposited having a thickness t ⁇ , the shape is maintained.
• a peak 11 in the form of a rectangular protrusion with a width 1 (as shown in the cross sectional view of Fig. 6a) and a thin layer 6a is deposited having a thickness t ⁇ , the shape is maintained.
• the height hi of the protrusion 11 is larger than the thickness ti this causes openings in the layer 6a, which effect may e.g. be exploited to manufacture membranes with well-defined pore (opening) sizes, filters and the like.
• the third scaling factor parameter ⁇ may be derived from measurements in the following manner.
• the Height-Height Correlation Function (HHCF) is defined as
• H ( r, t) ⁇ [hix + r. t) - ft ⁇ x r t)j 2 > ⁇ ⁇
• the uni-directional film deposition as described above, where the value of the dynamic exponent is very high (z>6) can be utilized for example for a deposition process to obtain a substrate structure 7 in the form of a super barrier films in the case the substrate 6 is very smooth and does not contain any particles or features.
• the uni-directional film deposition can also be utilized to obtain substrate structures 7 which act as highly selective membranes.
• An even further application of the embodiments of the present substrate structure 7 may be found in the patterning of an inorganic layer by depositing a film on a substrate 6 containing photoresist patterns, e.g. the protrusions 11 as shown in Fig. 6a. For example, suppose that the height hi in Fig 6a comprises a photoresist pattern.
• the substrates 6 used in this illustrative description has a thickness smaller than the gap distance g between the at least two opposing electrodes 2, 3 and may range from 20 ⁇ m to 800 ⁇ m, for example 50 ⁇ m or 100 ⁇ m or 200 ⁇ m and can be selected from: SiO 2 wafers, glasses ceramics, plastics and the like.
• layers of a chemical compound or chemical element can be deposited on substrates having a relatively low Tg, meaning that also common plastics, like polyethylene (PE), polypropylene (PP), Triacetylcellulose, PEN, PET, polycarbonate (PC) and the like can be provided with a deposition layer.
• Other substrates 6, 7 which can be chosen are for example UV stable polymer films such as ETFE or PTFE (from the group of fluorinated polymers) or silicone polymer foils. These polymers may even be reinforced by glass fibre to improve impact resistance.
• the substrates provided with the deposition according to the present invention can be used in a wide range of applications like wafer manufacturing, they can be used as barrier for plastics or applications where a conductive layer on an isolator is required and the like.
• the present invention embodiments can be used advantageously for producing substrates having properties suitable for applications in e.g. OLED devices, or more general for substrates in the form of films or foils which are usable for protecting against deterioration by water and/or oxygen and having smooth properties e.g. barrier films in the field of flexible PV-cells.
• the gas mixture applied for providing the present embodiments of substrate structures 7 includes a reactive gas and a precursor.
• oxygen as a reactive gas has many advantages also other reactive gases might be used like for example hydrogen, carbon dioxide, ammonia, oxides of nitrogen, and the like.
• the formation of a glow discharge plasma may be stimulated by controlling the displacement current (dynamic matching) using the plasma control unit 4 connected to the electrodes 2, 3, leading to a uniform activation of the surface of substrate in the treatment space 5.
• the plasma control unit 4 e.g. comprises a power supply and associated control circuitry as described in the pending international patent application PCT/NL2006/050209, and European patent applications EP-A-1381257, EP-A- 1626613 of applicant, which are herein incorporated by reference.
• the deposition may be stimulated by using heated substrate as described in WO2008/147184 of applicant, which is herein incorporated by reference. All illustrative examples have been prepared having a polymer 6 substrate temperature of90°C.
• precursors can be can be selected from (but are not limited to): W(C0)6, Ni(CO)4, Mo(CO)6, Co2(CO)8, Rh4(CO)12, Re2(CO)10, Cr(CO)6, or Ru3(CO)12, Bis(dimethylamino)dimethylsilane (BDMADMS), Tantalum Ethoxide (Ta(OC 2 H 5 ) 5 ), Tetra Dimethyl amino Titanium (or TDMAT) SiH 4 CH 4 , B 2 H 6 or BCl 3 , WF 6 , TiCl 4 , GeH4, Ge2H6Si2H6 (GeH3)3SiH, (GeH3)2SiH2, hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), 1,1,3,3,5,5- hexamethyltrisiloxane, hexamethylcyclotetrasiloxane, octamethyl
• the gas composition in the treatment space comprised nitrogen and oxygen and HMDSO (1000 mg/hr).
• the concentration of oxygen was varied in the treatment space. Table I:

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• 2009
  • 2009-06-11 GB GBGB0910040.5A patent/GB0910040D0/en not_active Ceased
• 2010
  • 2010-05-25 WO PCT/GB2010/050856 patent/WO2010142972A1/en not_active Ceased
  • 2010-05-25 US US13/318,238 patent/US20120052242A1/en not_active Abandoned
  • 2010-05-25 JP JP2012514535A patent/JP2012529765A/ja active Pending
  • 2010-05-25 EP EP10725839A patent/EP2440685A1/en not_active Withdrawn
• 2014
  • 2014-06-09 US US14/299,238 patent/US20150017339A1/en not_active Abandoned

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