• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Process for preparing copper oxide (I) layers on a metal oxide substrate. The present invention relates to a process for preparing layers of copper (I) oxide on a metal oxide substrate, in which organic solutions of a copper (II) salt are used as a precursor, and a treatment is carried out thermal in the presence of an inert gas and oxygen. It also refers to the architectures obtainable by said procedure, and the use thereof in photovoltaic applications. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2683913A2
    申请号:ES201730422
    申请日:2017-03-28
    公开日:2018-09-28
    发明作者:Alberto CALLEJA LAZARO；Ruben TAMAYO BUISAN
    申请人:Oxolutia S L；Oxolutia SL；
    IPC主号:
    专利说明:

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    Solution Application
    In the process of the invention, the solution of a copper (I) oxide precursor is applied to the metal oxide substrate by, for example, inkjet 5, inkjet, spraying, dip (dip coating) , or spin (spin coating). Preferably it is applied by inkjet.
    In this preferred embodiment of inkjet, the deposition of the solution of a precursor is effected by inkjet printheads, which
    10 allow the control of the surface density of drops that lead to the thicknesses of the desired layers after the heat treatment stage.
    Heat treatment
    In the process of the invention, once the copper oxide (I) precursor solution has been deposited on the metal oxide substrate, a heat treatment is carried out in a furnace, preheated to a temperature between 400 ° C and 1200 ° C, preferably between 700º C and 900º C, and more preferably about 800º
    C. The substrate, maintained at room temperature after application of the
    The solution of the precursor is introduced into the oven, usually using a heating ramp from room temperature to oven temperature, between 1 ° C / s and 100 ° C / s, preferably between 5 ° C / s and 50 ° C / s, more preferably between 8º C / s and 20º C / s, and even more preferably between 10º C / s and 15º C / s.
    During the heat treatment, a flow of inert gas is passed through the furnace, such as, for example, argon, xenon, or nitrogen, preferably nitrogen, comprising between 100 and 5000 ppm of oxygen, preferably 200 ppm, over a period of time. of time between 5 seconds and 60 minutes, preferably between
    30 1 minute and 20 minutes, more preferably between 8 minutes and 12 minutes, and even more preferably about 10 minutes. The inert gas flow is generally between 0.2 L / min and 1.2 L / min, preferably between 0.4 L / min and 0.8 L / min, and more preferably it is about 0.6 L / min , and even more preferably about 0.6 L / min of nitrogen.
    35 13
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    Architecture
    The architecture obtainable according to the process of the invention is also part of the object of the invention.
    In the process of the invention, with a first application of the metal precursor solution, an epitaxial layer of copper (I) oxide is obtained on a metal oxide substrate. On the other hand, if consecutive layers are applied, a polycrystalline layer of copper (I) oxide is obtained on said metal oxide substrate. Each of these laminar structures is called architecture.
    The epitaxial layers are characterized by measuring pole figures using an X-ray diffractometer with two-dimensional detector to analyze the crystallographic texture, such as the Bruker-AXS device, model D8 Advance, with an X-ray tube KFL, Cu 2K (Ȝ (CUKĮ) = 1.541840 Å, with conditions of 40 kV and 40 mA, and collimators of 0.05 mm, 0.1 mm, 0.3 mm and 0.5 mm.
    In this way you can access the angles ĭ (Phi) and ȋ (Chi), which are the polar coordinates of the pole figures. The pole figure is an angular distribution function of a given crystallographic direction with respect to the sample reference system. Stereographic projection allows both crystallographic directions and directions associated with the sample to be represented on a plane.
    Texture is a variable that characterizes the microstructure of materials, so that in materials science, crystallographic texture is the distribution of crystalline orientations in a polycrystalline. Said distribution results from the polycrystalline formation conditions.
    The process of the invention allows to prepare epitaxial layers of copper oxide
    (II) on textured metal oxides, as seen in Figures 1, 2 and 3, which are the pole figures of the architectures prepared in Examples 1, 2 and 3 according to the process of the invention.
    16
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    6.25% v / v of diethanolamine and 26% v / v of propionic acid of 99.5% purity, and kept stirring for a few minutes until complete homogenization.
    A substrate of strontium oxide and titanium (IV) (SrTiO3) doped with 0.5% was taken
    5 by weight of Nb (Nb: STO (100)) of dimensions of 5x5x0.2, expressed in mm, and washed with acetone using an ultrasonic bath, and was subjected to a plasma activation in a UVO-CLEANER device Model 42 SERIES (Jelight Company Inc.), for a period of approximately 10 minutes.
    10 Next, said substrate was placed in the center of the spinner, and a volume of 14 μL of the precursor solution prepared above was deposited thereon. To obtain a uniform distribution of said solution, an angular speed of 6000 rpm was applied with an acceleration of 3000 rpm / s for 2 minutes.
    15 Once the solution was distributed on the substrate, the coated substrate was placed at the end of a preheated tubular oven at a temperature of approximately 800 ° C, and introduced into the center of the oven with the help of a metal rod in 1 minute. The substrate was maintained for a period of approximately 10 minutes, during which a constant flow of 0.6 L / min of nitrogen was applied, with 200 ppm
    20 of oxygen.
    At this stage the decomposition of the organic matter by pyrolysis and the formation and epitaxial growth of the copper oxide (I) layer occurred. After 10 minutes, the sample was pushed from the center to the end of the oven with the
    25 help the rod, and let it cool to room temperature.
    The resulting layer of copper oxide (I) obtained was epitaxial, with a cube-on-cube growth with the reflection (200) on the face with the reflection (100) of the Nb: STO. Figure 1 shows the figure of poles corresponding to said layer, registered
    30 on the Bruker-AXS device, model D8 Advance, with an X-ray tube KFL, Cu 2K (Ȝ (CUKĮ) = 1.541840 Å, with conditions of 40 kV and 40 mA, and collimators of 0.05 mm , 0.1 mm, 0.3 mm and 0.5 mm.
    The obtained layer had a thickness between 20 and 200 nm. 35 18


    Example 2: Preparation of an epitaxial layer of copper (I) oxide on a
    substrate of strontium oxide and titanium (IV) doped with niobium (Nb: STO
    (111)) Following a procedure substantially analogous to that described in Example 1, epitaxial layer of copper (I) oxide was prepared from the copper (I) oxide precursor solution, described in the same example, on a Strontium titanium oxide (IV) substrate (SrTiO3) doped with 0.5% by weight of niobium (Nb: STO (111)).
    An epitaxial copper (I) oxide layer was obtained, with a growth of the face (110) of the copper (I) oxide on the face (111) of the Nb: STO. Figure 2 shows the figure of poles corresponding to said layer, registered under the same conditions as in Example 1.
    The obtained layer had a thickness between 40 and 300 nm.
    Example 3: Preparation of an epitaxial layer of copper (I) oxide on a
    monocrystalline magnesium oxide substrate (100) Following a procedure substantially analogous to that described in Example 1, epitaxial layer of copper (I) oxide was prepared on a magnesium oxide substrate on the face with reflection (100).
    The copper (I) oxide precursor solution was prepared by dissolving copper (I) acetate in n-butanol at a concentration of 0.47 M. To this solution was added 5.3% v / v diethanolamine, and kept stirring for a few minutes until complete homogenization.
    An epitaxial copper (I) oxide layer was obtained, with growth with reflection
    (110) on the face with the reflection (100) of magnesium oxide. Figure 3 shows the figure of poles corresponding to said layer, registered under the same conditions as in Example 1.
    The obtained layer had a thickness between 20 and 300 nm.
    19
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    权利要求:
    Claims (1)
    [1]
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    同族专利:
    公开号 | 公开日
    ES2683913B1|2019-08-13|
    ES2683913R1|2018-10-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP3190593B2|1997-03-27|2001-07-23|スター精密株式会社|Method for producing cuprous oxide film|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201730422A|ES2683913B1|2017-03-28|2017-03-28|PROCEDURE FOR PREPARING COPPER OXIDE LAYERSON A METAL OXIDE SUBSTRATE|ES201730422A| ES2683913B1|2017-03-28|2017-03-28|PROCEDURE FOR PREPARING COPPER OXIDE LAYERSON A METAL OXIDE SUBSTRATE|
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