Apparatus and method for producing a transformed crystalline layer from a solution

Abstract

A manufacturing apparatus (10) capable of manufacturing a conversion crystal layer from a conversion crystal layer growth solution includes a first wall (11) and a substrate (14) defining a crystal growth cavity (13) therebetween, at least one growth solution inlet / outlet device (12) for controlling the supply of growth solution to or the discharge of growth solution from the crystal growth cavity (13) over time, and a temperature setting device (15) for creating a temperature profile (15b) for the crystal growth cavity (13), the substrate (14), or the first wall (11). The temperature profile (15b) controls free growth of a conversion crystal layer from all or a portion of a formation surface (14a) of the substrate (14) facing into the crystal growth cavity (13), primarily in a direction transverse to the formation surface (14a), over a thickness of more than 1 micrometer. The entire thickness of the conversion crystal layer is obtained by the free growth of the conversion crystal layer.

Description

Technical Field

[0001] The present invention relates to an apparatus for producing a conversion crystal layer by a liquid process.

[0002] The present invention also relates to a method for producing a conversion crystal layer that implements such an apparatus.

Background Art

[0003] In the field of detectors for X-rays, gamma rays, or charged or uncharged particle radiation, particularly in the field of medical or nuclear imaging, it is important to detect as accurately as possible the amount of radiation emitted, received, or transmitted, typically the radiation received by a patient or the radiation passing through a patient. Therefore, in order to absorb the maximum amount of radiation, a thick layer of crystals, i.e., a conversion crystal thicker than 1 micrometer, is required. Depending on the intended application, it is also necessary for the conversion crystal layer to have a surface area ranging from a few square millimeters to several tens of square centimeters.

[0004] In this regard, for example, it is known to produce deposits in a liquid state by spin centrifugation or by other methods called "slot die" or "doctor blade". However, when these methods are applied to obtain a thin layer having a thickness of less than a micrometer, it is not possible to obtain a thick layer exceeding several tens of micrometers in thickness.

[0005] A known solution for obtaining a thick conversion crystal layer consists of using a supersaturated solution between two plates in order to grow crystals constrained between the two plates of a reactor for the purpose of obtaining a conversion crystal layer. This technique is called "space-limited inverse temperature crystallization".

[0006] Furthermore, a challenge with this solution is that the temperature and distribution of the supersaturated solution are not precisely controlled, resulting in growth that includes structural defects. Moreover, in this case, the thickness of the layer is determined by the distance between the two plates. This lack of control is all the more limited because this approach promotes growth within the plane of the layer being produced. Therefore, obtaining a large surface layer requires growth exceeding several tens of square centimeters, and without controlling the solution distribution and temperature, it is impossible to produce a layer of the quality necessary for detecting ionizing radiation. [Overview of the project] [Problems that the invention aims to solve]

[0007] The present invention aims to address all or part of the problems presented above.

[0008] In particular, it provides a solution that satisfies all or some of the following objectives: • To obtain a sufficiently thick layer of conversion crystal in optoelectronic devices. • To obtain control over the distribution and temperature in the solution. • To obtain a thick layer of conversion crystals of sufficient quality, which is a large surface layer, preferably larger than several square centimeters, and more preferably larger than about 10 square centimeters. [Means for solving the problem]

[0009] This objective can be achieved by a manufacturing apparatus that enables the production of a transformed crystal layer from a transformed crystal layer growth solution. This manufacturing apparatus is • A first wall and substrate that partition the crystal growth cavity between them, A device comprising at least one inlet / outlet for a growth solution, which controls, over time, at least one function selected from the group consisting of supplying the growth solution to a crystal growth cavity and discharging it from the crystal growth cavity, A temperature setting device that creates a temperature profile for at least one element selected from the group consisting of a crystal growth cavity, a substrate, and a first wall, Equipped with, The temperature profile controls the free growth of the transformation crystal layer over a thickness of more than 1 micrometer, primarily in a direction transverse to the formation surface of the substrate directed into the crystal growth cavity, from all or part thereof. The total thickness of the transformation crystal layer is obtained by the free growth of the transformation crystal layer.

[0010] Some preferred, but not limited, embodiments are as follows:

[0011] In one embodiment of the apparatus, the first wall is fixed to the substrate to seal it, so that the growth solution supplied to the crystal growth cavity by at least one inlet / outlet device is discharged from the crystal growth cavity through only at least one element selected from the group consisting of at least one inlet / outlet device and a spontaneous discharge port. The spontaneous discharge port is provided in the first wall or in the portion of the substrate located in the growth cavity.

[0012] In one embodiment of the apparatus, the temperature setting device includes an element that allows for changes in the temperature profile over time.

[0013] In one embodiment of the apparatus, the temperature setting device includes an element that can configure a temperature profile for at least one element selected from the group consisting of a crystal growth cavity, a substrate, and a first wall.

[0014] In one embodiment of the apparatus, the temperature profile created by the temperature setting device includes at least one temperature lower than the temperature of the substrate.

[0015] In one embodiment of the apparatus, the temperature profile created by the temperature setting device includes at least one temperature higher than the temperature of the substrate.

[0016] In one embodiment of the apparatus, the entirety or part of the temperature setting device is arranged in at least one element selected from the group consisting of a first wall, an inlet / outlet device for the conversion crystalline liquid precursor, and a second wall formed on the outer surface opposite to the substrate formation surface.

[0017] In one embodiment of the apparatus, the temperature setting device comprises a plurality of temperature control regions, each control region having a range temperature that can be changed by the temperature setting device, independently of the other control regions.

[0018] In one embodiment, the control device includes a plurality of independent inlet / outlet devices for the conversion crystal growth solution, arranged on both sides of the substrate parallel to the formation surface.

[0019] In one embodiment of the apparatus, at least one inlet / outlet device for the conversion crystalline liquid precursor is positioned facing the forming surface.

[0020] In one embodiment of the apparatus, the entire or partial surface of the formation surface includes a seed layer of conversion crystals.

[0021] In one embodiment of the apparatus, at least a portion of the substrate is formed by at least one pixel, The seed layer comprises a plurality of permeable or impermeable crystal grains, and in at least one pixel, the seed layer comprises at least one of the plurality of crystal grains.

[0022] In one embodiment of the apparatus, the seed layer has a crystal principal orientation along the axis {n00}, where n is an integer between 1 and 4.

[0023] In one embodiment of the apparatus, the seed layer has a crystal principal orientation along the axes of a group consisting of axes {110} and {111}.

[0024] In one embodiment of the apparatus, the temperature profile created by the temperature setting device is configured such that the conversion crystal layer is formed only on a limited portion of the substrate's formation surface so as not to contact the first wall, and the remaining portion of the formation surface lacks the conversion crystal.

[0025] In one embodiment of the device, at least one inlet / outlet device for the growth solution penetrates at least one element selected from the group consisting of the first wall and the substrate.

[0026] In one embodiment of the device, the conversion crystal layer to be formed is ABX3, A’2C D 3+ X6, A 4+ X6 and A2 3+ X9, and is a perovskite of a type selected from the group consisting of. Here, A, A’, C, D and B are cations, and X is a halogen anion.

[0027] In one embodiment of the device, the conversion crystal layer to be formed has the formula A for electronic neutrality ) 1-(y2+…+yn) A ( y2… A (n) yn B ) 1-(z2+…+zm) B ( z2… B (m) zm X ) 3-(x2+…+xp) X ( x2 … X (p) xp and is an organic-inorganic hybrid perovskite of. Here, A (n) and B (n) correspond to cations, and X (n) corresponds to a halogen anion.

[0028] In one embodiment of the device, the thickness of the conversion crystal layer to be manufactured is 100 micrometers or more.

[0029] The present invention also relates to a manufacturing method for manufacturing a conversion crystal layer from a conversion crystal layer growth solution on a substrate. The method is implemented in the above-described manufacturing apparatus, and the method includes the following steps.

[0030] a) A process of controlling over time at least one function selected from the group consisting of supplying the growth solution of the manufacturing apparatus to a crystal growth cavity partitioned between the first wall of the manufacturing apparatus and the substrate by a growth solution inlet / outlet device, and discharging it from the crystal growth cavity. b) A step of creating a temperature profile using a temperature setting device in at least one element selected from the group consisting of a crystal growth cavity, a substrate, and a first wall. c) A step of configuring a temperature profile that controls the free growth of a conversion crystal layer exceeding 1 micrometer in thickness, mainly in a direction transverse to the formation surface of a substrate directed into a crystal growth cavity, wherein the total thickness of the conversion crystal layer is obtained by the free growth of the conversion crystal layer.

[0031] In one embodiment of the method, in step c), the configuration of the temperature profile is changed over time.

[0032] In one embodiment of the method, in step c), a temperature profile is formed for at least one element selected from the group consisting of a crystal growth cavity, a substrate, and a first wall.

[0033] In one embodiment of the method, in step c), the temperature profile is configured such that the transformation crystal layer is formed only on a limited portion of the formation surface so as not to contact the first wall, and the remaining portion of the formation surface lacks the transformation crystal.

[0034] In one embodiment of the method, in step a), the manufacturing apparatus sequentially supplies several growth solutions of different properties into the crystal growth cavity via an inlet / outlet device.

[0035] In one embodiment of the method, the manufacturing apparatus includes a plurality of inlet / outlet devices, and in step a), several growth solutions of different properties are supplied to the crystal growth cavity simultaneously or sequentially from different inlet / outlet devices.

[0036] Other aspects, purposes, advantages, and features of the present invention will be better described below by reading the detailed description relating to preferred embodiments, which are made with reference to the accompanying drawings. These are given as non-limiting examples. [Brief explanation of the drawing]

[0037] [Figure 1] Figure 1 shows a cross-sectional view of an example of a manufacturing apparatus according to the present invention, in which the inlet / outlet device is located on the first wall, and the first wall is fixed to the substrate so as to be sealed by a joint. [Figure 2] Figure 2 shows a cross-sectional view of an example of a manufacturing apparatus according to the present invention, in which an inlet / outlet device is positioned on the first wall facing the forming surface, and two inlet / outlet devices are positioned on both sides of the substrate, parallel to the forming surface. [Figure 3] Figure 3 shows a cross-sectional view of an example of a manufacturing apparatus according to the present invention, in which two inlet / outlet devices are arranged on both sides of the substrate, parallel to the forming surface, and a converted crystal layer is formed on the forming surface. [Figure 4] Figure 4 shows a cross-sectional view of an example of a manufacturing apparatus according to the present invention, in which the temperature setting device is arranged along a surface smaller than the substrate. [Figure 5] Figure 5 shows a cross-sectional view of an example of a manufacturing apparatus according to the present invention, in which the temperature setting device has several control regions. [Figure 6] Figure 6 shows a cross-sectional view of an example of a manufacturing apparatus according to the present invention, in which the forming surface includes all or part of the seed layer of the transformed crystal layer. [Figure 7] Figure 7 shows a side view of an example of the manufacturing apparatus according to the present invention, where the temperature profile between the first wall and the substrate is highlighted. [Figure 8] Figure 8 shows a cross-sectional view of an example of a manufacturing apparatus according to the present invention, where the temperature profile between the first wall and the substrate is highlighted. [Figure 9]Figure 9 shows a perspective view of an example of a manufacturing apparatus according to the present invention, in which two inlet / outlet devices are arranged on both sides of the substrate, parallel to the forming surface. [Figure 10] Figure 10 shows a perspective view of an example of a manufacturing apparatus according to the present invention, in which four inlet / outlet devices are arranged on both sides of the substrate, parallel to the forming surface. [Figure 11] Figure 11 shows a perspective view of an example of a manufacturing apparatus according to the present invention, in which four inlet / outlet devices are arranged on both sides of the substrate, parallel to the forming surface. In addition, two more inlet / outlet devices are arranged facing the forming surface, separated by a first wall. [Figure 12] Figure 12 shows a flowchart of an example of a manufacturing method according to another aspect of the present invention. [Figure 13] Figure 13 shows an example of a manufacturing apparatus according to the present invention, in which a liquid precursor circulates through an accumulator, then through a pump system, is filtered and injected into a crystal growth cavity, and the residue retained by filtration is refilled into the accumulator. [Figure 14] Figure 14 is a top view showing an example of a substrate containing multiple pixels partially covered by a seed layer having permeable crystal grains. [Modes for carrying out the invention]

[0038] In the attached Figures 1-14 and the following description, functionally identical or similar elements are identified by the same reference numerals.

[0039] In addition, individual elements are not shown to scale for the purpose of clarifying the diagram to facilitate understanding.

[0040] Furthermore, different embodiments or examples, and their variations, are not mutually exclusive, but rather can be combined with each other.

[0041] Firstly, the present invention relates to a manufacturing apparatus 10 that enables the production of a transformed crystal layer by a liquid process.

[0042] The application areas are particularly the manufacture of X-ray or gamma-ray detectors, used for particle detection in large-scale scientific instruments in medical radiography, non-destructive testing, security, nuclear, astronomical, and physical sciences. However, these areas are not limited. For example, the manufacture of scintillators for converting X or gamma photons into visible photons is conceivable. The same applies to the manufacture of detectors for visible photons with wavelengths including 400-800 nanometers, or for other wavelengths of electromagnetic radiation such as near-infrared radiation with wavelengths exceeding 800 nanometers.

[0043] The conversion crystalline layer should be understood as one or more crystals that produce an electrical response when, for example, photons or charged or uncharged particles penetrate it. The crystals constituting the conversion layer may also be selected for their ability to absorb the energy radiation of X-rays, gamma rays, or charged or uncharged particles and convert them into other, more easily measurable radiation, depending on the application and their physical properties. The term "crystalline layer" refers to a single-crystal layer or a polycrystalline layer. Thus, a single-crystal layer consists of crystal grains having a single crystal orientation. A polycrystalline layer consists of aggregates of crystal grains with different crystal orientations.

[0044] The phrase "from the growth solution" is equivalent to "by a liquid process," and the transformation crystal layer should be understood as being obtained from one or more precursors (called solutes) dissolved in one or more solutions, which as a whole is in a liquid state, and is referred to in the following text as the transformation crystal layer growth solution. The growth of the transformation crystal layer in the growth solution can be accelerated by changing parameters such as the temperature of the growth solution.

[0045] In this text, "growth solution" and "liquid precursor" are considered equivalent.

[0046] The principle by which the transformation crystal layer is formed in solid form is that the dissolved precursor is configured to be in a supersaturated state, and this state can be induced by a predetermined temperature. In other words, the solute concentration (the precursor of the transformation crystal layer dissolved in the solution) needs to be slightly higher than the solubility limit in the solvent, for example, on the order of a few percent, such as 5%, and this forms a growth solution in a supersaturated state. In this state, the formation of transformation crystals from the growth solution is thermodynamically favorable.

[0047] The supersaturation of the solute in the growth solution is determined by parameters such as temperature, solute concentration of the conversion crystal, solvent properties, use of non-solvents, or pressure. The conditions necessary for growth are known to those skilled in the art. When temperature is used as the driving force, in the case of retrograde solubility, crystallization is achieved by increasing the temperature. In this case, solubility decreases as the temperature rises. In the case of direct solubility, crystallization is achieved by decreasing the temperature. Therefore, by accurately setting the temperature profile in the manufacturing apparatus, it is possible to select where and when crystallization of the conversion crystal layer occurs.

[0048] Conversely, it may be advantageous to temporarily maintain the solute in an unsaturated state, where the solute concentration of the conversion crystal is slightly lower than the solubility limit, on the order of 1%. In this state, the conversion crystal of the already formed crystal layer or the seed layer 17 can be dissolved. Such partial dissolution is preferable because it can eliminate specific structural defects. Therefore, it is desirable to obtain a crystal surface with fewer defects and stresses before the subsequent growth process, which takes place in a supersaturated state of the solute (precursor of the conversion crystal layer).

[0049] The manufactured transformation crystal layer may be a hybrid perovskite such as CH3NH3PbBr3, which combines organic and inorganic parts. Alternatively, it may be an all-inorganic perovskite such as CsPbBr3. Preferably, A follows the rules of electronic neutrality. (1) 1-(y2+…+yn) A (2) y2… A (n) yn B(1) 1-(z2+…+zm) B (2) z2… B (m) zm X (1) 3-(x2+…+xp) X (2) x2… X (p) xp It has a general chemical formula ABX3, including a mixed composition such as A. (n) corresponds to an organic or inorganic cation, B (n) is a metal ion (e.g., Pb 2+ Sn 2+ ) corresponds to X (n) is a halogen anion (Cl - , Br - , I - ) corresponds to, thereby inducing the formation of an octahedral structure in which the ion beams related to each site A, B, and X are connected by vertices. The indices n, m, and p are integers. The indices x, y, and z are different molar percentages. Some examples of compositions are shown below: MAPbI3, MAPbCl3, MAPbI 3-x Br x MAPbBr 3-x Cl x MA y GA 1-y PbI3, FAPbBr3, CsPbBr3, Cs2AgBiBr6, CsFAPbI3, Cs y FA 1-y PbI 3-x Br x , Cs 1-y-z MA y FA z PbI 3-x Br x MA is methylammonium [CH3NH3] + In response to this, FA is homulamidinium [HC(NH2)2] + In response to this, GA is guanidinium [C(NH2)3] + It corresponds to.

[0050] Other perovskite structures are also possible, for example, A'2C 1+ D 3+ X6, A2B 4+ X6, or A3B23+ X9 may also be X9. A, A', C, D, and B are cations, B is in particular a metallic cation, and X is a halogen anion. A, A', B, C, D, and X are single elements or mixtures of at least two elements.

[0051] The conversion crystal layer produced, as described above, may be ionic or nonionic and may be doped with organic or inorganic additives. The conversion crystal layer produced may be formed according to other configurations similar to perovskite. For example, it may be a configuration such as vacant ordered double perovskite, 2D layered perovskite, perovskite-like material, defective perovskite, elpasolite, or double perovskite. Finally, other types of materials such as Ruddlesden-Popper, Dion-Jacobson, chalcogenite, or Rudorffites may constitute the conversion crystal layer.

[0052] The solvent used may be a mixture of solvents. Preferably, the solvent is polar and aprotic. For example, it may be N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, N-methyl-2-pyrrolidone, etc.

[0053] As shown in Figure 1-6, the manufacturing apparatus 10 includes a first wall 11 and a substrate 14 that separate the crystal growth cavity 13 between them. A growth solution is supplied to the crystal growth cavity 13. The growth solution is supplied to the crystal growth cavity 13 and discharged from there.

[0054] The substrate 14 may be an inert surface that functions solely as a support, or it may be a functionalized surface for an optoelectronic device, as shown in Figure 14, or it may be a matrix of active or passive elements of a detector including transistors.

[0055] In the examples illustrated in Figures 1-6, the first wall 11 is fixed to the substrate 14 to seal it, and as a result, the growth solution supplied to the crystal growth cavity, controlled by the inlet / outlet device 12, is then discharged from the crystal growth cavity 13 either by the discharge-controlled inlet / outlet device 12 or only by spontaneous discharge. Spontaneous discharge may take the form of overflow, or, for example, an opening for a siphon provided in the first wall 11, or a siphon provided for this purpose in, for example, a portion of the substrate 14 located in the growth cavity 13. The term "spontaneous discharge" should be understood as a free and natural flow without any device intended to alter the flow. The advantage of this is reduced implementation costs.

[0056] In other words, there should be no undesirable leakage of the solution between the first wall 11 of the crystal growth cavity 13 and the substrate 14, that is, at the connection point between the two.

[0057] For example, a joint can be provided between the first wall 11 and the substrate 14. This joint is preferably chemically inert to the solvent used to dissolve the liquid precursor. The material may be, for example, Teflon® or Kalrez®. In another example, the joint may be created by depositing an adhesive joint such as silicone, or by welding the first wall 11 onto the substrate 14 with a low-melting-point, chemically inert thermoplastic resin such as polypropylene. In this case, the joint must be created and destroyed each time new growth occurs. If the joint must be destroyed, it can be removed mechanically, chemically, thermally, or using light.

[0058] In one example, the joint is fixed to the first wall 11 but not to the substrate 14. This allows the first wall 11 on the substrate 14 to be moved between each growth stage.

[0059] In examples not shown, the retaining system can mechanically hold at least the first wall 11 and the substrate 14 by maintaining pressure at the intersection between the first wall 11 and the substrate 14, thereby preventing leakage between the first wall 11 and the substrate 14. The retaining system may be, for example, a flange, a screw device, or even a weight.

[0060] In this invention, growth occurs only on one surface of the substrate and in the region of interest. Crystallization on the back surface or periphery of the substrate, such as uneven nucleation on raised areas of the substrate, which can occur in uncontrolled ways, such as when the substrate is completely immersed, does not occur.

[0061] The first wall 11 can be formed from a material such as glass, fluoropolymer (PTTF®), or polypropylene.

[0062] Furthermore, as shown in Figures 1 to 6 and Figures 8 to 11, the manufacturing apparatus 10 may also include at least one growth solution inlet / outlet device 12. This device controls over time at least one of the functions of supplying the growth solution to the crystal growth cavity 13 and discharging the growth solution from there. The growth solution inlet and outlet should be understood to mean that the growth solution is injected into or out of the crystal growth cavity, corresponding to the word "supplied," or drawn out, corresponding to the word "discharged." These functions may be performed sequentially by inlet / outlet devices 12, or by different inlet / outlet devices 12, each performing only one function.

[0063] Similarly, the flow rates at the inlet and outlet of the growth solution can be modified in the substrate to adjust the supply of dissolved precursors, i.e., solutes, within the crystal growth cavity 13 and / or on each face of the transformation crystal layer being formed. The same inlet / outlet device 12 may perform two injection and suction functions sequentially. In one example, one inlet / outlet device 12 is located in the wall of the crystal growth cavity 13 for injection of the growth solution, and a free liquid outlet, i.e., an uncontrolled, spontaneous flow, in other words, an always-open opening, is located in the first wall 11 or the substrate 14 for discharge of the solution from the crystal growth cavity 13. Preferably, several inlet / outlet devices 12 are formed through the wall of the crystal growth cavity 13, each having one liquid injection or discharge function. The injection and discharge nozzles thus formed can be spatially distributed and temporally synchronized to facilitate the circulation of the liquid within the crystal growth cavity 13. In this text, the terms “nozzle” and “inlet / outlet device” are equivalent.

[0064] The changes over time include, for example, a change from a growth solution supply function to a growth solution discharge function in accordance with the growth of the conversion crystal, a change in the flow rate of the growth solution, and a change from a pass-through mode (injection, extraction, or discharge) to a blocked state. Preferably, the changes over time consist of opening and closing an inlet / outlet device 12 that performs only one of the functions of injection, discharge, and extraction, and are performed independently and spatially, depending on the nozzle position and time (injection, discharge, and extraction), in order to properly agitate the liquid in the cavity. The advantage of this is that the flow and spatial arrangement of the liquid precursor can be adapted according to the growth of the conversion crystal.

[0065] As shown in Figures 2-6 and 8-11, multiple inlet / outlet devices 12 for the growth solution are arranged on both sides of the substrate 14, parallel to the forming surface 14a. The inlet / outlet devices 12 may have two, three, or multiple openings, such as a shower. Inlet / outlet devices 12 for the liquid precursor may be provided on all sides of the reaction cavity 13, independently of their injection or discharge properties.

[0066] In other examples shown in Figures 2 and 11, at least one of the growth solution inlet / outlet devices 12 is positioned facing the forming surface 14a. In this example, the inlet / outlet device 12 may have two, three, or multiple openings, such as a shower. This allows for uniform growth. Thus, it can be considered that the growth solution is injected through the first wall 11 of the crystal growth cavity via the laterally positioned inlet / outlet device 12, and the growth solution is discharged through the inlet / outlet device 12 positioned facing the forming surface 14a.

[0067] Therefore, the growth solution enters and exits the crystal growth cavity, depending particularly on the arrangement, flow rate, and pressure of the inlet / outlet device 12 in the manufacturing apparatus 10. This circulation is preferable because it maintains a uniform concentration of the dissolved precursor of the transformation crystal throughout the growth front, i.e., the interface between the formed transformation crystal layer and the solution. This is preferable for 20 cm³. 2 This method is particularly preferable for larger surfaces, and it allows for obtaining a transformed crystal layer in which grain boundaries are as uniform as possible and which has good homogeneity with respect to grain thickness.

[0068] The transformed crystal layer can be grown using a liquid precursor under pressure, which, on the one hand, provides parameters that are expected to affect solubility other than temperature, and on the other hand, promotes the circulation of the growth solution within the crystal growth cavity 13. Therefore, this makes it possible to avoid the problem of solute (precursor) supply at the crystal layer-growth solution interface (growth front), which can cause instability in crystal growth.

[0069] The growth of the transformed crystal layer may be stopped or reduced by fluctuations in the flow rate of the growth solution and / or changes in temperature.

[0070] Preferably, the inlet / outlet device 12 is positioned and driven to circulate the liquid precursor through the growth of the thick conversion crystal layer at the growth front, which is the surface of the thick conversion crystal layer parallel to the substrate plane. Thus, the liquid precursor circulates over a surface equivalent to the target detection area. In fact, throughout the object of the present invention, growth is preferably carried out directly in situ in the radiation detection or conversion device. This is advantageous compared to devices that mechanically constrain growth between two plates. In fact, in these devices, the solution cannot circulate over the surface of the conversion crystal layer covering the detection area, but can only circulate at the lateral growth front of the crystal layer.

[0071] The inlet / outlet device 12 can consist of, for example, solution inlet and outlet nozzles arranged to ensure a sufficient and uniform flow of the growth solution across the entire growth surface of the transformed crystal layer. Such an arrangement, unlike systems designed for, for example, inter-plate growth, can minimize dead zones without fluid renewal.

[0072] It may be considered that several growth solutions or solutes with different properties, i.e., dissolved precursors, can be introduced simultaneously or sequentially through different inlet / outlet devices 12, or sequentially through the same inlet / outlet device 12.

[0073] In other words, the introduction of two different liquid precursors, i.e., growth solutions with different properties, into the crystal growth cavity 13 can be carried out sequentially without purging between them. In another example, the first growth solution can be injected alone first, and then the first growth solution and a second growth solution with different properties can be injected simultaneously through different inlet / outlet devices 12, or they can be injected through the same inlet / outlet device 12, and then the second growth solution can be injected alone. A first transformation crystal layer having the first properties is deposited to a predetermined thickness, and then the solution supply line is purged, for example, with an inert gas. Subsequently, by changing the properties of the precursor / growth solution, a second transformation crystal layer having the second properties can be obtained on top. According to this example, if the respective crystal lattice parameters allow it, several compounds can be deposited on top of each other. By purging between each compound with a neutral gas (Ar, N2), the transition from one crystal to another is not contaminated by the ambient air. In the case of perovskites, for example, it is possible to deposit multiple layers based on MAPbI3, MAPbBr3, MAPbCl3, or other perovskite compositions such as solid solutions, in an order determined by those skilled in the art. This multilayer configuration is advantageous for modifying the interface at electrode contacts that may be included in the areas on the substrate 14 where growth is considered. This can be done by locally modifying the interface at the valence band and conduction band levels, i.e., the energy barrier to charge injection. Furthermore, this allows the surface of the resulting thick transformation crystal layer to be passivated with a perovskite structure less sensitive to the environment, such as phenethylammonium or butylammonium lead halide BA2PbX4 type. The layer in contact with the substrate can also be made to have mechanical properties that minimize mechanical stress caused by the difference in thermal expansion between the substrate 14 and the resulting thick perovskite layer.

[0074] In one example, the growth solution does not completely fill the crystal growth cavity 13. The height of the growth solution can also be adjusted. This allows for the control, and even cessation, of the growth of the conversion crystal layer if necessary.

[0075] In another example, the inlet / outlet device 12 can inject an inert gas (argon, nitrogen) into the crystal growth cavity 13, for example, or into the growth solution before supplying the growth solution to the crystal growth cavity 13. This allows for degassing and purging of the supply lines of the inlet / outlet device 12 and the accumulator 70 in the manufacturing apparatus 10 before growing the conversion crystal layer using a neutral gas. This allows for control of conditions such as humidity, oxygen, or ozone levels.

[0076] The manufacturing apparatus 10 further comprises a temperature setting device 15 for creating a temperature profile within at least the crystal growth cavity 13 and / or the substrate 14 and / or the first wall 11. An example of the temperature profile 15b is schematically shown in Figures 7 and 8. The temperature profile 15b may consist of a temperature gradient between the substrate 14 and the first wall 11, or between the formed transformation crystal layer and the first wall 11. The temperature profile is variable and adjusted over time. For example, it may be adjusted in accordance with the progress of the growth of the transformation crystal layer, either in a predetermined manner or by continuous thickness measurement. That is, growth may be controlled in real time using a camera capable of continuously measuring the thickness of the growing layer, or by Fizeau interferometry. In this configuration, a feedback loop may be configured for the temperature of a localized region to control uniform growth over time across the desired surface.

[0077] The temperature profile 15b controls the free growth of the transformation crystal layer over a thickness of more than 1 micrometer, mainly in a direction transverse to the formation surface 14a of the substrate 14 directed into the crystal growth cavity 13, from all or part of the formation surface 14a.

[0078] In a desirable example, the growth temperature is kept below 80°C to minimize the difference in thermal expansion between the thick layer of the transformation crystal and the substrate.

[0079] In this text, free growth is equivalent to growth without constraints and external physical stresses from opposing each other. Free growth is distinctly different from crystal growth obtained, for example, between two plates separated from each other in a small space where growth is confined and guided parallel to the two plates. Such constraints cause mechanical stress due to the crystal layer being confined between the two plates during temperature changes, which is detrimental to crystal quality. Thus, free growth is different from the growth of crystals or polycrystals that are mechanically constrained between two walls and can only grow in one growth direction or a specific possible growth direction. In other words, free growth is achieved when a transformation crystal layer grows from the substrate but does not encounter walls that are positioned facing the substrate and inhibit growth, at least in the thickness direction.

[0080] In this invention, the entire thickness of the transformation crystal layer is obtained by the free growth of the transformation crystal layer. This is preferable because it allows the crystal layer to grow transversely to the substrate rather than parallel to it. This arrangement is also desirable because it allows the crystal layer to be obtained in situ in the transverse direction at a desired location on the substrate.

[0081] The term "formation" is equivalent to crystallization, which results in growth, homoepitaxy, heteroepitaxy, and the formation of polycrystalline layers.

[0082] In the example shown in Figure 5, the temperature setting device 15 can set the temperature below the substrate and / or at the first wall and / or at the inlet / outlet device 12 and, optionally, at the inlet of the growth solution to which they are connected, with a high precision of 0.1°C, preferably 0.01°C. As shown in Figures 7 and 8, this configuration makes it possible to adjust the temperature of the growth solution before it enters the crystal growth cavity 13 and to construct the thermal geometry (geometrie thermalique) in the growth region. By setting the temperature of the growth solution in the crystal growth cavity 13, for example, by maintaining it at a temperature higher than the saturation equilibrium in the case of retrograde solubility and at a temperature lower than the saturation equilibrium in the case of direct solubility, growth can be maintained over time. Thus, the temperature profile 15b generated by the temperature setting device 15 includes at least one temperature lower than the temperature of the substrate 14 in the case of direct solubility. In one example, a temperature gradient normal to the substrate can be established within the crystal growth cavity 13. The temperature profile that refines the supersaturation profile of the solution can also be modulated in time and / or space according to the growth of the transformed crystal layer. Therefore, the supersaturated profile can move within the crystal growth cavity 13 in accordance with the growth of the conversion crystal layer. By time modulation of the temperature gradient, normal growth on the substrate can be maintained, and the thickness of the crystal layer can be set by the duration of growth. This thickness can also be set by the position of the saturation limit set within the cavity. Once formed, the conversion crystal layer has a thickness of preferably more than 1 micrometer, preferably more than 100 micrometers, and more preferably more than 300 micrometers. In the case of a direct conversion X-ray detector, the thickness of the manufactured conversion crystal can be determined, depending on the application, to absorb more than 85% of the incident radiation at the target energy.

[0083] For example, to achieve absorption equivalent to that of CsI (which absorbs 85% of X-rays in RQA5 and 50% in RQA9) at 600 micrometers, a 600-micrometer thick CH3NH3Pbl3, or a 1300-micrometer thick CH3NH3PbBr3 in RQA5 (according to IEC62220-1, with an X-ray spectrum centered at 50 keV), and a 450-micrometer thick CH3NH3Pbl3, or an 800-micrometer thick CH3NH3PbBr3 in RQA9 (according to IEC62220-1, with an X-ray spectrum centered at 70 keV).

[0084] Furthermore, the temperature profile can also be adjusted to suppress the growth of the transformed crystal layer on the sides of the transformed crystal layer, as shown in Figure 8. That is, the temperature profile can be configured such that the solution is supersaturated only in the direction across the substrate 14, and not supersaturated on the sides of the transformed crystal layer. This is desirable to obtain a transformed crystal layer with a thickness of several micrometers, preferably several hundred micrometers, and where the transformed crystal layer is maintained according to markings provided at specific locations on the substrate 14. That is, in the example shown in Figure 3, the temperature setting device 15 is set such that the transformed crystal layer is formed only on a limited portion of the forming surface 14a of the substrate 14, without contact with the first wall 11, and the rest of the forming surface 14a lacks transformed crystals. Aspect ratios of 1 to 1400 between the thickness of the transformed crystal and its spread on the substrate are achievable and desirable. In one example, the resulting crystal layer can reach a thickness of 300 micrometers for a lateral dimension of 40 centimeters. Achieving such aspect ratios is not easy in techniques that do not include means for creating a temperature profile that allows for the induction of the growth of the transformed crystal layer according to a specific configuration.

[0085] In the example shown in Figure 5, all or part of the temperature setting device 15 is positioned at least at the first wall 11 and / or the inlet / outlet device 12 for the conversion crystal liquid precursor and / or the second wall 16 formed on the outer surface of the substrate 14 opposite to the formation surface 14a. This arrangement is desirable because it allows for precise adjustment of the temperature profile in time and space. That is, the growth solution is temperature-controlled in a manner distinct at the interface with the formed conversion crystal layer and at the interface with the first wall 11, so that growth is promoted only in the conversion crystal layer. It is also possible to set and modify the temperature profile in time and space to favor the growth of the conversion crystal layer in the thickness direction.

[0086] In a complementary example, the temperature setting device 15 comprises multiple control regions 15a, each control region 15a having a region temperature that can be independently modified by the temperature setting device 15 relative to the other control regions 15a. This configuration is desirable as it allows for precise adjustment of the temperature profile in both time and space. These control regions 15a can be positioned in any direction in space.

[0087] In one example, the temperature setting device 15 includes a Peltier-type module, which can be used to obtain a temperature lower than that of the liquid precursor or to cool the liquid precursor.

[0088] During crystallization, the supersaturated state of the growth solution can be maintained by changing its temperature over time. Ideally, layer growth / crystallization should occur at a constant temperature and concentration. In this case, it is necessary to compensate for the decrease in the concentration of the solute / precursor involved in layer growth in the passage to the growth cavity. In fact, the concentration of the dissolved precursor decreases due to partial crystallization at the layer surface.

[0089] In the example shown in Figure 13, the growth solution is obtained by dissolving, for example, a feeder body made of excess solid perovskite in a reaction chamber attached to a crystal growth cavity, which may be an accumulator 70. It is necessary to maintain a constant temperature difference between the accumulator 70 and the crystal growth cavity 13. The growth solution is drawn out by a pump system 71, filtered by 72, and then supplied to the crystal growth cavity 13. The growth solution then either flows back to the accumulator 70 by circulation or remains in the closed circuit again, becoming precursor / solute-rich. The residue 73 (held by the filter) is introduced back into the accumulator 70. This configuration of the manufacturing apparatus 10 makes it possible for 100% of the feeder body dissolved by the accumulator 70 to be deposited on the substrate in the form of conversion crystals, which has advantages in manufacturing cost and better control of the initial moment of the conversion crystal layer. This control device is in a closed circuit, making it easy to control the atmosphere, such as humidity, oxygen, or ozone levels.

[0090] For example, to accelerate growth, it may be advantageous to raise or lower the temperature of the liquid precursor before injecting it into the reaction cavity.

[0091] Growth on the substrate 14 can be performed without any specific processing of the substrate and is initiated spontaneously by temperature differences on the substrate. Alternatively, it can be advantageously initiated from a pre-formed seed layer 17.

[0092] In the example shown in Figure 6, the entire or partial surface 14a comprises a transformation crystal seed layer 17. This seed layer initiates the growth of the transformation crystal layer by homoepitaxy or heteroepitaxy, limiting spontaneous growth on unwanted surfaces. The seed layer may have the same properties as the transformation crystal layer or different properties.

[0093] When a seed layer is used, the crystal grains that constitute it must be oriented to promote the growth of the desired crystal axis along an axis normal to the plane of the substrate. For example, for MAPbBr3, if a person skilled in the art desires that the axis extending perpendicular to the substrate be in the {100} orientation, then the crystal grains of the seed layer should be oriented along the same axis as much as possible, in other words, they should follow the crystal principal orientation. "As much as possible" should be understood as the ratio of peak areas {nn0} / {n00} and {nnn} / {n00} for n=1, 2, 3, and 4, based on the θ / 2θ X-ray diffraction pattern, being less than 2%, preferably less than 0.5%, and more preferably less than 0.1%. The seed layer may be continuous or discontinuous, that is, it may consist of permeable or impermeable crystal grains (17a). The growing principal axes may be different, for example, {110} or {111}, but the ratio to note remains the same. The crystal principal orientation should be understood as equivalent to the "desired orientation".

[0094] The present invention makes it possible to control the conditions that promote the growth of the transformed crystal layer, particularly by adapting the thermal geometric shape and regenerating the solution in the cavity. The described manufacturing apparatus can achieve, and is desirable, the homogeneous growth of all crystal grains in the seed layer. Homogeneity should be understood as the same growth rate on the growth surface for all crystal grains, regardless of their position on the substrate. Therefore, if the orientation of the crystal grains constituting the seed layer is controlled and they all have the same crystal orientation perpendicular to the substrate (overall symmetry C n, n=1, 2, 3...∞), the number of crystal grains in the final thick transformation crystal layer is equal to the number of crystal grains in the seed layer. All crystal grains grow at the same rate and in the same direction, and none outgrow their surroundings. This has two main advantages. The entire growth front is planar, and the grain boundaries are perpendicular, and their number is the same as in the seed layer. The uniformity of the thickness of the transformation crystal layer favorably contributes to the uniformity of the detector's photoelectric conversion efficiency. In other words, the number of crystal grains in the thick layer can be controlled by correctly controlling the crystal grains present in the nucleation layer. In particular, the crystal grains can have lateral dimensions ranging from a few micrometers to several hundred micrometers. They may be permeable or scattered. An important parameter is the crystal grain density per unit area. In the thick transformation crystal layer, grain boundaries behave differently from other parts of the layer from an electronic standpoint, especially due to the presence of structural defects that generate electron traps or ion transfer regions. When a transformation crystal layer is fabricated on a detector formed, for example, from pixels 14c, if these regions corresponding to grain boundaries cross several pixels 14c, these pixels 14c will behave differently from others, and the presence of grain boundaries may be visualized, for example, in X-ray radiography images. For this reason, it is desirable for the crystal layer to contain several crystal grains per pixel 14c, thereby homogenizing the performance of each pixel 14c and eliminating the visibility of grain boundary traces in the image. In other words, this allows for the averaging of electronic disturbances related to grain boundaries across pixels. Pixels 14c can have lateral dimensions ranging from a few micrometers to several hundred micrometers. These dimensions are typically 80 to 200 micrometers in medical applications. On the surface of the thick layer in contact with the pixels, it is preferable that each pixel has at least one crystal grain, more preferably two or three crystal grains belonging to a single pixel, which corresponds to 80 grains / mm² for a square pixel with sides of 150 micrometers. 2 This corresponds to a density exceeding [a certain value]. A more desirable density is when more than 5 crystal grains belong to a single pixel, which corresponds to 200 grains / mm for a square pixel with sides of 150 micrometers. 2This corresponds to a density exceeding a certain level. Controlling the grain density per pixel is achieved by controlling the deposition conditions of the nucleation layer, such as the drying rate of the layer.

[0095] The present invention allows for the advantageous crystallization of the converted crystal layer by contacting the substrate with a smaller amount of liquid precursor compared to known methods in which the substrate is immersed in a solution. This advantage is more pronounced in the embodiment shown in Figure 13. Here, unlike when the substrate is immersed, several layers can be formed sequentially without compromising purity. This represents a significant benefit in terms of production time and cost.

[0096] In one example, the substrate 14 can be thermally annealed in a controlled atmosphere or under vacuum within the crystal growth cavity 13 before contacting it with the liquid precursor. This removes water molecules adsorbed on the surface of the substrate 14.

[0097] A photoelectron device, not shown in the figures, can be manufactured from the conversion crystal layer obtained by the manufacturing apparatus 10 of the present invention. To manufacture this photoelectron device, an upper electrode is deposited. Preferably, the electrode is deposited continuously on at least the entire surface of the active matrix covered by the conversion crystal layer. In one example, a single upper electrode common to all pixels of the matrix is ​​deposited. This electrode may have the same properties as the lower electrode that constitutes the substrate portion for obtaining the conversion crystal layer on top of it, or it may have different properties, as in a photodiode device. Metals (Au, Cr, Pt, Pd, Ag), conductive oxides (ITO, AZO, GZO), conductive organic materials (PEDOT-PSS, PANI, graphite, carbon ink), or laminations of these materials may be used. Furthermore, one or more interface layers may be used on the electrode, for functional purposes or for chemical compatibility with the perovskite (PEIE, C60, MoO3, V2O5, BCP, SPIRO). The upper electrode is then electrically connected to an external circuit, for example, via a conductive wire or a conductive line created by printing.

[0098] The conversion crystal layer is finally encapsulated in air, or in an inert atmosphere (N2, Ar), or in an anhydrous atmosphere. This is done using a glass cover connected to the surface of the portion of the substrate not covered by the conversion crystal layer. This involves using adhesive beads or adhesive, a pressure-sensitive adhesive, and a resin film containing a barrier layer. The encapsulation is transparent or opaque to visible light but transmits the radiation to be detected.

[0099] Subsequently, the connection pads of the pixel matrix are connected to the readout electronic component using piping and an ACF (Anisotropic Conductive Film) type adhesive. The matrix may be characterized by a typical readout method of the pixel imaging device.

[0100] The present invention also relates to a method for producing a transformed crystal layer on a substrate 14 from a growth solution, in other words, by a liquid process. This method is carried out by a manufacturing apparatus 10 as in the example described above.

[0101] As shown in Figure 12, the method includes the following steps.

[0102] a) A step of controlling, depending on time and nozzle position, the supply of the growth solution to and discharge from the growth cavity 13 partitioned between the first wall 11 of the reactor / manufacturing apparatus 10 and the substrate 14 by the inlet / outlet device 12 of the manufacturing apparatus 10.

[0103] b) A step of creating a temperature profile 15b using a temperature setting device in at least the crystal growth cavity 13 and / or the substrate 14 and / or the first wall 11.

[0104] c) A step of configuring a temperature profile that controls the free growth of a conversion crystal layer exceeding 1 micrometer in thickness, preferably in a direction transverse to the formation surface 14a of the substrate 14 directed into the crystal growth cavity 13, from all or part of the formation surface 14a of the substrate 14.

[0105] This method allows for the control of the formation of a uniformly distributed grain boundary conversion crystalline layer with a thickness greater than 1 micrometer, more preferably greater than 100 micrometers, as described in detail in the preceding paragraphs. The method of the present invention also allows the growth of the conversion crystalline layer from a surface determined by the substrate 14 in a direction transverse to the substrate 14. Thus, the conversion crystalline layer grows preferably, in other words, primarily, in one direction transverse to the substrate 14. The phrase "primarily" should be understood to mean that similarly, more than 80%, preferably more than 95%, of the crystalline mass grows in the transverse direction. In practice, parasitic crystals may occur irregularly and undesirably at the edges of the substrate. The method of the present invention differs from growth methods limited to between two closed surfaces. To cover a surface exceeding several square centimeters, these methods perform growth in a direction parallel to the two surfaces, not in a direction transverse to the substrate, and growth transverse to the two surfaces is impossible because it is blocked by the two surfaces.

[0106] In one example, in step c), the temperature profile 15b is changed over time. This allows the process to adapt to the saturation state of the liquid precursor, for example, as the thickness of the transformed crystal layer increases.

[0107] In an additional example, in step c), the temperature profile 15b is formed at least in the crystal growth cavity 13 and / or the substrate 14 and / or the first wall 11. This configuration allows for precise control of the temperature profile that governs the growth of the transformed crystal layer. In fact, growth depends on the supersaturation state of the growth solution and the local temperature values ​​at the crystal layer-solution interface.

[0108] In an additional embodiment, in step c), the temperature profile 15b is configured such that the transformation crystal layer is formed only on a limited portion of the forming surface 14a without contacting the first wall 11, and the remaining portion of the forming surface 14a lacks transformation crystals. This configuration can limit the generation of parasitic crystals that cause short circuits. It can also promote the growth of the transformation crystal layer only in terms of its thickness.

[0109] In an additional embodiment, in step a), several growth solutions of different properties are sequentially supplied into the crystal growth cavity 13 by the inlet / outlet device 12.

[0110] In one embodiment, the manufacturing apparatus 10 includes a plurality of inlet / outlet devices 12, and in step a), several growth solutions of different properties are supplied into the crystal growth cavity 13 simultaneously or sequentially by a different inlet / outlet device (12).

[0111] These embodiments allow for the modification of electrode interfaces that may be included in the areas where growth is considered on the substrate 14, which is desirable. This is done by locally modifying the interfaces at the valence and conduction band levels, i.e., the energy barriers to charge injection.

[0112] This also allows for the passivation of the surface of the resulting thick transformation crystal layer by crystallizing a perovskite structure that is less sensitive to the environment.

[0113] The layer in contact with the substrate can also be made to have mechanical properties that minimize the mechanical stress caused by the difference in thermal expansion between the substrate 14 and the resulting thick layer of perovskite.

[0114] The temperature setting device 15 described above may also be configured in other ways, particularly as part of the manufacturing apparatus 10, to create a temperature profile 15b. For this purpose, the temperature setting device 15 may comprise multiple thermally controllable elements to form the temperature profile 15b and, if necessary, obtain a desired thermal geometric shape in the growth region.

[0115] For example, each thermally controllable element may be selected from heating elements, cooling elements, and in particular, elements configured to be selectable for heating and cooling. The heating element may be resistive so as to achieve a temperature strictly higher than the ambient temperature, which is, for example, between 20°C and 120°C. The cooling element may be a thermoelectric conversion element such as a Peltier type. The element configured for heating or cooling may be a thermoelectric conversion module such as a Peltier type, which may be capable of selectively performing heating and cooling modes, thereby allowing adjustment of the operating mode. The existence of thermally controllable elements as described makes possible a region of uniform temperature (a set of thermally controllable elements that enable heating or cooling) and a clear temperature gradient (a combination of a thermally controllable element that heats and another thermally controllable element that cools). For the production of photoelectric crystals, that is, for the production of a transformation crystal layer in the growth region, several thermally controllable elements as described above, positioned on the opposite side of the crystal growth cavity 13 of the substrate 14, can define a region of uniform temperature perpendicular to the normal direction of the surface of the substrate 14 (i.e., a region of uniform temperature in the plane parallel to the surface of the substrate 14).

[0116] As a result, the thermally controllable elements can partition the control region 15a described above.

[0117] The operational control point of a thermally controllable element can be adjusted by measuring the temperature profile obtained on the surface of the substrate 14. For example, the temperature profile obtained on the surface of the substrate 14 can be measured non-contact by infrared temperature measurement or by using a thermocouple.

[0118] To limit the crystallization region (in other words, the growth region), the thermally controllable elements can be arranged to form a first set of thermally controllable elements and a second set of thermally controllable elements. The thermally controllable elements in the second set of thermally controllable elements are close to the thermally controllable elements in the first set of thermally controllable elements. The thermally controllable elements in the second set of thermally controllable elements can form a lateral temperature gradient. This involves giving the thermally controllable elements in the second set of thermally controllable elements a first operational control point, which is significantly different from the operational control point of the thermally controllable elements in the first set of thermally controllable elements. "Significantly different" should be understood to mean that the two temperature control points differ by a range of several degrees to tens of degrees. "Lateral temperature gradient" should be understood to mean that the gradient is realized in a plane parallel to the plane of the substrate 14. Again, by measuring the temperature profile on the surface of the substrate 14, the operational control points of the thermally controllable elements in the first set of thermally controllable elements can be adjusted to obtain the most significant possible lateral temperature gradient, which enables crystallization. Conversely, the operational control points of the thermally controllable elements in the second set of thermally controllable elements can be adjusted, which tends to prevent crystallization.

[0119] Similarly, thermally controllable elements placed within and / or around the cell, at the top and bottom of the cell, can form a thermogeometric shape suitable for growth in a direction perpendicular to the substrate surface (i.e., the direction in which the thickness of the substrate 14 is measured). The cell includes a first wall 11 that partitions the crystal growth cavity 13 between it and the substrate 14. By combining these thermally controllable elements with the thermal conductivity of the cell, the substrate 14 and the top of the cell can be made to have different temperatures, and consequently, crystallization on the substrate 14 can be limited to a predetermined volume. In this paragraph, the concepts of top and bottom are given according to an axis having a height away from the substrate 14 toward the wall 11, and the axis ends above the substrate 14. The volume, and more specifically the thickness, in which crystallization is possible is therefore, • Controlled by the control point temperature of a thermally controllable element, • Depends on the thermal conductivity of the cell.

[0120] Therefore, a desirable temperature profile perpendicular to the surface of the substrate 14 is obtained by adjusting the control points of the thermally controllable elements, and the obtained profile is controlled by local temperature measurements using thermocouples. The presence of one or more thermally controllable elements in the cell enables heating of the growth solution and provides circulation of the heated growth solution.

[0121] The first wall 11 may be made of a metallic material (such as aluminum or copper), and may be coated with a chemically inert material if necessary, or it may be made of a resin material (such as polytetrafluoroethylene).

[0122] The substrate 14 may be made of glass or a resin such as polyamide.

Claims

1. A manufacturing apparatus (10) that enables the production of a converted crystal layer from a converted crystal layer growth solution, wherein the manufacturing apparatus (10) A first wall (11) and a substrate (14) partition the crystal growth cavity (13) between them, At least one inlet / outlet device (12) for the conversion crystal layer growth solution controls over time at least one function selected from the group consisting of supplying the conversion crystal layer growth solution to the crystal growth cavity (13) and discharging it from the crystal growth cavity (13), The system includes a temperature setting device (15) that creates a temperature profile (15b) for at least one element selected from the group consisting of the crystal growth cavity (13), the substrate (14), and the first wall (11), The temperature profile (15b) controls the free growth of the transformation crystal layer over a thickness of more than 1 micrometer, mainly in a direction transverse to the formation surface (14a) of the substrate (14) directed into the crystal growth cavity (13). The total thickness of the transformation crystal layer is obtained by free growth without contact with the first wall (11) of the transformation crystal layer, in a manufacturing apparatus (10).

2. In the manufacturing apparatus (10) of claim 1, The first wall (11) is fixed to seal against the substrate (14), thereby the conversion crystal layer growth solution supplied to the crystal growth cavity (13) by the at least one inlet / outlet device (12) is discharged from the crystal growth cavity (13) only through elements selected from the group consisting of the at least one inlet / outlet device (12) and the first wall (11) or a portion of the substrate (14) located within the crystal growth cavity (13), in a manufacturing apparatus (10).

3. In the manufacturing apparatus (10) of claim 1 or 2, The manufacturing apparatus (10) includes an element that allows the temperature setting device (15) to be changed over time.

4. In any one of the manufacturing apparatus (10) according to claims 1 to 3, The manufacturing apparatus (10) includes an element that allows setting the temperature profile (15b) for at least one element selected from the group consisting of the crystal growth cavity (13), the substrate (14), and the first wall (11).

5. In any one of the manufacturing apparatus (10) according to claims 1 to 4, The temperature profile (15b) created by the temperature setting device (15) includes at least one temperature that is lower than the temperature of the substrate (14) in the manufacturing apparatus (10).

6. In any one of the manufacturing apparatus (10) according to claims 1 to 4, The temperature profile (15b) created by the temperature setting device (15) includes at least one temperature that is higher than the temperature of the substrate (14) in the manufacturing apparatus (10).

7. In any one of the manufacturing apparatus (10) according to claims 1 to 6, A manufacturing apparatus (10) wherein all or part of the temperature setting device (15) is positioned on at least one element selected from the group consisting of the first wall (11), the inlet / outlet device (12) for the transformation crystal layer growth solution, and the second wall (16) formed on the outer surface of the substrate (14) opposite to the forming surface (14a).

8. In any one of the manufacturing apparatus (10) according to claims 1 to 7, The manufacturing apparatus (10) comprises a temperature setting device (15) with a plurality of control regions (15a), each of which has a range of temperatures that can be changed by the temperature setting device (15) independently of the other control regions (15a).

9. In any one of the manufacturing apparatus (10) according to claims 1 to 8, A manufacturing apparatus (10) comprising a plurality of independent inlet / outlet devices (12) for the conversion crystal layer growth solution, arranged parallel to the forming surface (14a) on both sides of the substrate (14).

10. In any one of the manufacturing apparatus (10) according to claims 1 to 9, A manufacturing apparatus (10) wherein at least one of the inlet / outlet devices (12) for the conversion crystal layer growth solution is positioned facing the forming surface (14a).

11. In any one of the manufacturing apparatus (10) of claims 1 to 10, A manufacturing apparatus (10) in which the entirety or part of the forming surface (14a) includes the seed layer (17) of the conversion crystal layer.

12. In the manufacturing apparatus (10) of claim 11, At least a portion of the substrate (14) is formed from at least one pixel (14c), The seed layer (17) comprises a plurality of permeable or impermeable crystal grains (17a), Manufacturing apparatus (10), wherein in at least one pixel (14c), the seed layer (17) includes at least one crystal grain of the plurality of crystal grains.

13. In the manufacturing apparatus (10) of claim 11 or 12, The seed layer (17) has a crystal principal orientation along the axis {n00}, where n is an integer between 1 and 4, in the manufacturing apparatus (10).

14. In the manufacturing apparatus (10) of claim 11 or 12, The seed layer (17) has a crystal principal orientation along the axes of a group consisting of axes {110} and {111}, in the manufacturing apparatus (10).

15. In any one of the manufacturing apparatus (10) according to claims 1 to 14, The temperature profile (15b) created by the temperature setting device (15) is configured such that the conversion crystal layer is formed only on a limited portion of the forming surface (14a) of the substrate (14) so ​​as not to come into contact with the first wall (11), and the remaining portion of the forming surface (14a) is devoid of the conversion crystal layer, in the manufacturing apparatus (10).

16. In any one of the manufacturing apparatus (10) according to claims 1 to 15, The manufacturing apparatus (10) has at least one inlet / outlet device (12) for the conversion crystal layer growth solution that penetrates at least one element selected from the group consisting of the first wall (11) and the substrate (14).

17. In any one of the manufacturing apparatus (10) according to claims 1 to 16, The formed conversion crystal layer is ABX ３ 、A’ ２ C １＋ D ３＋ X ６ 、A ２ B ４＋ X ６ 、and A ３ B ２ ３＋ X ９ 、is a perovskite of a type selected from the group consisting of, and A, A’, C, D and B are cations and X is a halogen anion, production apparatus (10).

18. In any one of the manufacturing apparatus (10) according to claims 1 to 16, The transformed crystal layer formed is related to the electronic neutrality of formula A （１） １－（ｙ２＋…＋ｙｎ） A （２） ｙ２… A （ｎ） ｙｎ B （１） １－（ｚ２＋…＋ｚｍ） B （２） ｚ２… B （ｍ） ｚｍ X （１） ３－（ｘ２＋…＋ｘｐ） X （２） ｘ２… X （ｐ） ｘｐ It is an organic-inorganic hybrid perovskite, A （ｎ） and B （２） is a cation and X （ｎ） A manufacturing apparatus (10) in which halogen anions are represented.

19. In any one of the manufacturing apparatus (10) described in claims 1 to 18, A manufacturing apparatus (10) in which the thickness of the manufactured conversion crystal layer is 100 micrometers or more.

20. A manufacturing method for producing a converted crystal layer on a substrate (14) from a converted crystal layer growth solution, wherein the manufacturing method is carried out using a manufacturing apparatus (10) according to any of claims 1 to 19. a) A step of controlling over time at least one function selected from the group consisting of supplying the conversion crystal layer growth solution of the manufacturing apparatus (10) to the crystal growth cavity (13) partitioned between the first wall (11) of the manufacturing apparatus (10) and the substrate (14) by the inlet / outlet device (12) of the manufacturing apparatus (10), and discharging it from the crystal growth cavity (13), b) A step of creating a temperature profile (15b) using a temperature setting device for at least one element selected from the group consisting of the crystal growth cavity (13), the substrate (14), and the first wall (11), c) A step of configuring the temperature profile (15b) that controls the free growth of a conversion crystal layer exceeding 1 micrometer in a direction mainly across the formation surface (14a) of the substrate (14) directed into the crystal growth cavity (13), wherein the total thickness of the conversion crystal layer is obtained by the free growth of the conversion crystal layer, and the step of configuring the temperature profile (15b), A manufacturing method that includes this.

21. In the manufacturing method of claim 20, A manufacturing method wherein, in step c), the configuration of the temperature profile (15b) is changed over time.

22. In the manufacturing method of claim 20 or 21, A manufacturing method wherein, in step c), the temperature profile (15b) is formed for at least one element selected from the group consisting of the crystal growth cavity (13), the substrate (14), and the first wall (11).

23. In any one of claims 20 to 22, A manufacturing method wherein, in step c), the temperature profile (15b) is configured such that the conversion crystal layer is formed only on a limited portion of the forming surface (14a) of the substrate (14) so ​​as not to come into contact with the first wall (11), and the remaining portion of the forming surface (14a) is devoid of the conversion crystal layer.

24. In any one of claims 20 to 23, A manufacturing method wherein, in step a), several of the conversion crystal layer growth solutions having different properties are sequentially supplied into the crystal growth cavity (13) by the inlet / outlet device (12).

25. In any one of claims 20 to 23, The manufacturing apparatus (10) is equipped with a plurality of inlet / outlet devices (12), A manufacturing method wherein, in step a), several of the conversion crystal layer growth solutions having different properties are supplied into the crystal growth cavity (13) simultaneously or sequentially, each by a different inlet / outlet device (12).

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