OPTOELECTRONIC DEVICE AND MANUFACTURING METHOD FOR AN OPTOELECTRONIC DEVICE
20230337454 · 2023-10-19
Assignee
- MICROOLED (GRENOBLE CEDEX 09, FR)
- Commissariat A L'energie Atomique Et Aux Energies Alternatives (Paris, FR)
Inventors
- Gunther HAAS (ST EGREVE, FR)
- Benoit DUGRENIL (Grenoble, FR)
- Sébastien GUILLAMET (LYON, FR)
- Myriam TOURNAIRE (GRENOBLE CEDEX 9, FR)
- Tony Maindron (Grenoble Cedex 9, FR)
Cpc classification
H10K71/30
ELECTRICITY
H10K50/131
ELECTRICITY
International classification
H10K71/20
ELECTRICITY
Abstract
An optoelectronic device that includes a substrate and a stack of organic layers that has at least one active layer arranged between a reflective surface and a semi-reflective surface arranged facing one another at a given distance and forming an optical cavity. The device includes at least three groups of pixels, each group of which is characterized by a cavity of a different optical length, the cavity having a number of bilayers arranged between the substrate and said stack of organic layers, each bilayer being formed of a first transparent and conductive layer of a first transparent and conductive material, and of a second transparent and conductive layer of a second transparent and conductive material, in direct contact with the first transparent and conductive layer.
Claims
1-14. (canceled)
15. An optoelectronic device, comprising: a substrate; a stack of organic layers comprising: at least one active layer to serve as a light-emitting layer or a photodiode, disposed between a reflective surface or a surface of a transparent layer deposited directly on said reflective surface, and a semi-reflective surface disposed facing one another at a given distance and forming an optical cavity of a given optical length, at least three groups of pixels, each group in the at least three groups of pixels having a cavity of a different optical length, the cavity comprising a plurality of bilayers arranged between the substrate and the stack of organic layers, each bilayer being formed by a first transparent conductive layer formed of a first transparent conductive material and a second transparent conductive layer formed of a second transparent conductive material in direct contact with the first transparent conductive layer, the first transparent conductive material being different than the second transparent conductive material, wherein: for a first group of pixels in the at least three groups of pixels, the number of bilayers is zero, for a second group of pixels in the at least three groups of pixels, the number of bilayers is one, for a third group of pixels in the at least three groups of pixels, the number of bilayers is one or two, when the number of bilayers is one the first layer of the bilayer associated therewith has a thickness that is greater than a thickness of the bilayer of the second group of pixels, for each additional group of pixels in the at least three groups of pixels, if present, the number of bilayers increases by one with respect to a previous group or remains the same, when the number of bilayers remains the same, the first layer of the bilayer associated therewith has a thickness that is greater than a thickness of a preceding group of pixels, the optical length of the cavity increases in numerical order of the at least three groups of pixels, for each bilayer, the first conductive transparent layer, counted from the substrate, has a lower resistance to a wet etching treatment than the second conductive transparent layer, and for each group of pixels beyond the first group of pixels, at least said first layer of the bilayer farthest from the substrate is protected laterally by the second layer of the bilayer.
16. The optoelectronic device of claim 15, wherein for each group of pixels beyond the first group of pixels, said first layer of the bilayer farthest from the substrate is totally encapsulated by the second transparent conductive layer.
17. The optoelectronic device of claim 15, wherein for each group of pixels beyond the first group of pixels, said first layer of all the bilayers is totally encapsulated by the second transparent conductive layer.
18. The optoelectronic device of claim 15, wherein the reflective surface is covered by a layer of the second transparent conductive material.
19. The optoelectronic device of claim 15, wherein in each of said bilayers, said first transparent conductive layer has a specific etching rate that is at least one thousand times greater than a specific etching rate of the second transparent conductive layer.
20. The optoelectronic device of claim 15, wherein the first transparent conductive material is selected from a group formed by: ZnO, oxides containing ZnO that are doped with gallium, and/or aluminum, and/or boron, and/or beryllium, indium oxide, and oxide containing indium oxide and which are doped with tin.
21. The optoelectronic device of claim 20, wherein said second transparent conductive material is selected from a group formed by: SnO.sub.2, and SnO.sub.2 that is doped with arsenic and/or with fluorine, and/or nitrogen, and/or niobium, and/or phosphorus, and/or antimony, and/or aluminum, and/or titanium.
22. The optoelectronic device of claim 15, wherein said stack of organic layers is in direct contact with the reflective surface or the transparent layer, and/or, the semi-reflective surface.
23. The optoelectronic device of claim 22, wherein said stack of organic layers is in direct contact with the semi-reflective surface.
24. The optoelectronic device of claim 15, wherein said stack of organic layers forms a continuous coating over all pixels in the at least three groups of pixels.
25. The optoelectronic device of claim 24, further comprising a semitransparent conductive layer deposited above said stack of organic layers which also forms a continuous coating over all pixels in the at least three groups of pixels.
26. The optoelectronic device of claim 15, wherein the substrate comprises a CMOS-type substrate having electrical circuits that facilitate an individual reading of the pixels in the at least three groups of pixels.
27. The optoelectronic device of claim 15, wherein the optoelectronic device comprises an OLED microdisplay.
28. The optoelectronic device of claim 15, wherein the optoelectronic device comprises a multispectral light sensor.
29. A method of manufacturing method an optoelectronic device comprising: depositing a first transparent conductive layer formed of a first transparent conductive material on a reflective surface; depositing a first mask that defines and protects a location of a second group of pixels and a third group of pixels; removing the first transparent conductive layer by wet etching at locations not protected by the first mask, the non-protected locations including a location for a first group of pixels, removing the first mask after removing the first transparent conductive layer; depositing a second transparent conductive layer formed of a second transparent material; depositing a third transparent conductive layer formed of the first transparent conductive material; depositing a second mask that defines and protects a location of the third group of pixels; removing the third transparent conductive layer is removed by wet etching at locations not protected by the second mask, the non-protected locations including a location for the first group of pixels and the second group of pixels; removing the second mask after removing the third transparent conductive layer; depositing a fourth transparent conductive layer formed of the second transparent conductive material; depositing a third mask that defines and protects a location of the first group of pixels, the second group of pixels; and removing the second transparent conductive layer, the fourth transparent conductive layer, the reflective layer and, the transparent layer by dry etching at the locations not protected by the third mask.
30. The method of claim 29, further comprising: depositing a filling element in spaces between neighboring pixels; depositing a stack of organic layers that is common to all the pixels; depositing a semi-reflective electrode layer that is common to all the pixels above the stack of organic layers.
31. The method of claim 29, wherein depositing the second transparent conductive layer and the fourth transparent conductive layer is conducted by atomic layer deposition.
32. The method of claim 29, wherein the wet etching treatment comprises a treatment with an aqueous solution of tetramethylammonium hydroxide at 2.38% by weight at ambient temperature.
Description
DRAWINGS
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DESCRIPTION
Unsuccessful Attempts to Solve the Problem Addressed
[0102] The inventors have realized that the solutions based on the use of structured dielectric layers as optical spacers require complex methods, such as the creation of conductive vias (in electronics, in an integrated circuit, a via is a metallized hole through an insulating layer which allows to establish an electric link between two levels of metal) or the use of methods of the thermal transfer type. For the same reason, the inventors have ruled out the use of the elements of the dielectric multilayer type.
[0103] The inventors have attempted to take as a starting point the solutions based on the use of conductive transparent layers (TCO, for example ITO, ZnO, SnO.sub.2) as an optical spacer, as described in particular in the document EP 1 450 419 cited above. However, the practical creation of the structure described in this document turned out to be very difficult, for several reasons.
[0104] Firstly, to be able to guarantee stable primary colors through the substrate (which is typically a silicon wafer having a diameter of 200 mm or 300 mm, with circuits prepared by the CMOS technology which are configured to address the pixels), a very good uniformity of the thickness of the optical cavities, of approximately 98% to 99%, is required, which is difficult to achieve with deposition methods as described in the prior art, such as cathode sputtering or chemical vapor deposition (CVD, or PECVD, i.e. Plasma Enhanced Chemical Vapor Deposition). However, the use of the ALD (Atomic Layer Deposition) technique allows to obtain such a homogeneity of the thickness. However, it can only be applied to a limited number of TCO materials, such as ZnO, AZO (which is a more conductive alternative of ZnO), as well as SnO.sub.2.
[0105] Secondly, the creation of three structured layers of TCO to form groups of pixels with three different optical thicknesses turns out to be rather difficult. As indicated above, European Patent Publication No. EP 1 672 962 includes the detailed description of a method based on three steps of deposition and of photolithography of resin, an etching and a stripping of these three layers of resin. With several additions and modifications, this can be translated into a process flow diagram shown by the images
[0106] The starting point is a substrate of the CMOS type (for example on a silicon wafer), with as a last level the metal for forming the pixels, here aluminum coated with a fine layer of TiN as protection against oxidation.
[0107] In a first sequence of steps illustrated in
[0108] On the second layer of TiN 15, three layers of TCO 16, 18, 20 (AZO or ZnO) were successively deposited by ALD (states in
[0109] It is noted that
[0110] In a second sequence of steps illustrated in
[0111] In a third sequence of steps illustrated in
[0112] In a fourth sequence of steps illustrated in
[0113] It was found that this method is not usable in industrial production, for three reasons.
[0114] First of all, the control of the final thickness of the TCO layers is not satisfactory. Although the deposition by ALD allows to control the thickness of the TCO layers with a precision of 1% - 2%, and leads to a very good uniformity over the surface area of the substrate, this thickness is reduced during the structuration method. It is in particular the step of stripping the photosensitive resin (i.e. the step that leads to the structure shown in
[0115] Then, it is observed that the edge of the pixel is degraded. Indeed, during the step that leads from the state (c) to the state (d) in
[0116] And finally, it is observed that the characteristic of the OLED pixel is degraded. With respect to a use of the original pixel metal (Al/TiN), it is found that the operating voltage of the OLED (deposited on the structure with the structured TCO layers) is increased from 1V to 2V, which is caused by a poor injection of the carriers (holes) of the TCO layer in the OLED.
[0117] In order to improve the control of the thickness, another type of TCO was used, in this case SnO.sub.2, which turned out to be significantly more resistant to wet etching than the TCOs of the ZnO or AZO type. Another advantage of the SnO.sub.2 is that it does not degrade the characteristics of the OLED stacks. However, the inventors were not able to find a method of wet etching allowing to completely remove the vertical walls created during the method of ALD deposition. Consequently, this new approach does not allow to solve the problem addressed: this combination of the teachings of the documents EP 1 450 419 and EP 1 672 962 leads to an impasse.
Description of Certain Embodiments of the Invention
[0118] It is retained from the experiment described above that to develop a method that allows good control of the final thickness and good homogeneity of the pixel without degradation of the edge the structure of the device must be modified. It is also retained that depositions of TCO by ALD on the photosensitive resin must be avoided, since this leads to the formation of vertical walls at the edge of the pixel, and that hardening of the photosensitive resin by dry etching, which makes it very resistant to stripping, must be avoided.
[0119] According to an essential feature of the present invention, a stack of at least two different layers of TCO, which differ by their resistance to etching, in particular to wet etching, are used as an optical spacer: the “hard” TCO is more resistant to etching than the “soft” TCO.
[0120] The soft TCOs, among which are found in particular ZnO and AZO, are etched very well via wet etching with a dry stripping of the photosensitive resin, for example via O.sub.2 plasma, after, and this does not affect their thickness. However, they must be protected during the step of dry etching to separate the pixels, and during the wet stripping of the photosensitive resin. It is noted that their use as an anode for the OLED also leads to an increase in the operating voltage.
[0121] The hard TCOs, among which is found in particular SnO.sub.2, are very resistant in particular to wet etching, and they can be etched only by dry etching. Moreover, they function well as an anode for the OLED stack, with a perfect conservation of the operating voltage compared to an anode made of Al/TiN.
[0122] According to this essential feature of the invention, a layer of soft TCO is mainly used as an optical spacer, but this layer is protected by a fine layer of hard TCO that also provides the interface towards the stack of organic layers of the device (OLED layers or photosensitive layers).
[0123] The concept of “soft” and “hard” TCO refers here to a reference wet stripping treatment (also called wet “etching” treatment), usually used in microelectronics, namely a stripping with an aqueous solution of tetramethylammonium hydroxide (CAS N°: 75-59-2) at 2.38% by weight; such a product is commercially available, for example from the company ThermoFischer Scientific™ (electronic grade, catalogue n° 44940). This wet etching is typically carried out at ambient temperature. According to this concept of “soft” and “hard” TCO, a “hard” TCO is a TCO that resists significantly better to such a wet etching treatment than a “soft” TCO, this resistance being able to be expressed by the specific etching rate in identical conditions. In the context of the present invention, regardless of the chemical nature of these layers of TCO, they must be selected with respect to one another in such a way that this difference in resistance to said reference wet etching treatment is respected. It should be specified that in the present context, the terms “hard” and “soft” do not refer to mechanical characteristics, but only to the resistance to wet etching.
[0124] Of course, the invention is not limited to TCOs that are “hard” and “soft” with respect to this reference treatment indicated above. In the method according to the invention it is possible to use other products and etching methods, which must nevertheless be selected in such a way that the TCOs that are, with respect to one another, respectively, “soft” and “hard” in the conditions of the reference treatment be also, with respect to one another, respectively, “soft” and “hard” in the conditions of the etching treatment chosen.
[0125] In the same optoelectronic device according to the invention, it is not necessary for all the layers of “hard” TCO to have the same chemical composition, and for all the layers of “soft” TCO to have the same composition, provided that in the wet etching conditions selected in the method according to the invention that are used by a given step, the layers of TCO in question behave like a layer of hard TCO and like a layer of soft TCO.
[0126] It is known that the resistance of a TCO can depend on the deposition technique. In the context of the present invention, an advantageous deposition technique is the technique of atomic layer deposition (ALD).
[0127] Preferably, in the context of the present invention, the hard TCO, the soft TCO and the etching treatment are chosen in such a way that the etching rate of the hard TCO is less than a tenth of the etching rate of the soft TCO, more preferably less than a hundredth, and even more preferably less than a thousandth.
[0128] For the soft TCO the etching rate (typically expressed in nm/min) must be adapted to the wet etching method used. If the etching rate is too high, the time between the end of the etching and the rinsing risks inducing an overetching difficult to control; the etching rate depends on the chemical nature of the TCO, its deposition method and the nature of the etching treatment (in particular the etching agent, its concentration and the temperature).
[0129] Typically, the “soft” TCOs usable for carrying out the present invention are TCOs containing ZnO, this ZnO being able to be doped, for example with gallium (oxide called GZO), with aluminum (AZO), with boron, and/or with beryllium. Another typical “soft” TCO system is the TCO containing indium oxide, which can be doped, in particular with tin; such an oxide known by the acronym ITO (Indium Tin Oxide) is widely used in microelectronics and optoelectronics. ITO cannot be deposited by ALD; indium oxide can be deposited by ALD, but this is a rather difficult method to control to guarantee correct stoichiometry.
[0130] Typically, the “hard” TCOs usable to carry out the present invention are TCOs containing SnO.sub.2, this SnO.sub.2 being able to be doped, for example with arsenic, with fluorine, with nitrogen, with niobium, with phosphorus, with antimony.
[0131] A first embodiment is described here with two groups of pixels of a different color, designated here by R and G.
[0132] In reference to
[0133] The lower reflective electrode 152 is deposited on this layer of insulant 151. This lower electrode 152 can include one or more layers. It can for example be made of silver, aluminum, copper, chromium or another metal with strong reflectivity, and in this case a single layer can suffice. It can also include several layers, as was described above and as illustrated in
[0134] In a first sequence of steps of the method according to the invention schematically illustrated in
[0135] Said fine layer of hard TCO which protects the lower electrode 152 is visible in
[0136] As illustrated in
[0137] In a third sequence of steps the wet etching of the layer 156 of soft TCO is carried out. In the case mentioned above in which a layer of hard TCO was interposed between the upper surface of the lower electrode and the first layer of soft TCO, the former layer is not removed by said wet etching treatment.
[0138] Then the photosensitive resin 158 is removed by a dry method, which is typically an oxygen plasma; this results in the structure schematically shown in
[0139] In a fourth step a second layer 160 of TCO is deposited. This layer must be significantly more resistant to the wet etching than the layer of soft TCO 156; for this reason this layer is called a layer of “hard” TCO. As indicated above, a layer of SnO.sub.2 can for example be used. The resulting structure is schematically illustrated in
[0140] In a fifth sequence of steps a structured deposit 162 of photosensitive resin is created on this layer 160 of TCO, in such a way that the spacing d.sub.2 between two neighboring zones 162a, 162b of photosensitive resin correspond to the spacing between two neighboring pixels R, G. This is schematically illustrated in
[0141] In a sixth sequence of steps the dry etching of all of the layers 160 of hard TCO, of possible residues of the soft TCO layer 156 and of the reflective electrode 152 is carried out to separate the pixels, followed by a wet stripping of the photosensitive resin 162. Said dry etching is advantageously carried out by RIE (Reactive-Ion Etching) or IBE (Ion Beam Etching). A structure schematically illustrated in
[0142] In a seventh sequence of steps a filling element 164 is deposited in the space between two neighboring pixels, for example by photolithographic techniques. This is schematically illustrated in
[0143] In an eighth sequence of steps the OLED stack 170, common to all the pixels, and a semi-reflective upper electrode 166 (also called top electrode) which is also common to all the pixels are deposited on this structured surface. This is schematically illustrated in
[0144] An optoelectronic device with two groups of pixels 167a, 167b is thus obtained, each group of pixels having an optical cavity of a different optical thickness, designated d.sub.R and d.sub.G, respectively. The optical cavities are formed between the lower electrode 152 of the pixel, which is reflective, and the semitransparent and semi-reflective electrode 166 at the top. The organic stack can be according to the destination of the optoelectronic device an emissive stack of the OLED type or a stack of the organic photodiode type. In this case, one of the pixels 167a is formed on a TCO layer that is formed from two layers 156, 160 of different TCO materials, one 156 soft, the other 160 hard, while the other of the pixels 167b is formed on a TCO layer that is only formed from a single layer 160 of TCO, which is a hard layer.
[0145] It is noted that even if the layer of TCO can be composed of two chemically different layers 156, 160, it acts in this optoelectronic device as a single optical spacer, and in this function it is designated here by the reference number 157 (visible in
[0146] This device can be used to create a display screen with two primary colors, for example red (R) and green (G). It can also be used to create a light detector responding in two different spectral zones; in this case all the optical paths are inverted and the light-emitting OLED stack 170 is replaced by a light-detecting stack of layers.
[0147] It is observed that the dry etching of the sixth step is a directional etching that removes the hard TCO 160 in the space having a width d2 between two neighboring zones (see the passage from
[0148]
[0149]
[0150] The optical thicknesses d.sub.R and d.sub.G, as well as the optical position of maximum intensity of the emitting layer 175, z.sub.y, are chosen so as to form for the pixels of the group G 167b a cavity that allows to extract a maximum of green light in the direction of the normal, and for the pixels of the group R 167a a maximum of red light. For this an OLED stack 170 emitting for example a spectrum with a peak in the yellow zone (abbreviated Y here) of the visible spectrum can be created.
[0151] Instead of using an OLED stack 170 with an emission peak in the yellow zone of the visible spectrum, an OLED stack 1700 with two different emitting layers 1751, 1752, in this case R and G, can also be used; such a device is illustrated in
[0152] It is also possible to use an OLED stack of the tandem type, either with two Y cells (schematically illustrated in
[0153] The structure of the stacks of the tandem type is illustrated in
[0154] The optical thicknesses d.sub.l, I=R, G are defined as the sum of the thicknesses e multiplied by the optical index n of all the layers that are located between the upper surface of the electrode 152 and the lower surface of the electrode 166. For example, with respect to
[0155] In these equations the index of each parameter refers to the numerical reference used in
[0156] In the same way, the optical position of the emission z.sub.J, J=Y, R, G is defined as the sum of the thicknesses e multiplied by the optical index n of all the layers that are located between the position of maximum intensity of emission of the corresponding emitting layer and the lower surface of the electrode 166. For example with respect to
[0157] In this equation the index of each parameter refers to the numerical reference used in
[0158] For example, in the geometry of
[0159] In relation to
[0160] The first part of the method is analogous to that which was described above for the device with two colors, until the fourth sequence of steps inclusive, with a set of photolithography masks adapted to a geometry with three different groups of pixels. After the fourth sequence of steps, an intermediate product schematically shown in
[0161] Then a second layer 3562 of soft TCO is deposited on the entire structure, as illustrated in
[0162] Then a second layer 3602 of hard TCO is deposited on the entire structure, to arrive at the structure illustrated in
[0163] Then the layer of photosensitive resin 3620 is removed by a wet stripping method and the structure illustrated in
[0164] It is noted, like in the first embodiment described in relation to
[0165] Moreover, as visible in
[0166] A device according to the invention can be used to create a display screen with three primary colors, for example red (R), green (G) and blue (B), in order to create a color screen of the type known by the name “full color”. For this, several embodiments are possible. For example an OLED stack 470 can be created comprising an assembly 575 of three different emissive layers 5712, 5710, 5711 emitting a white spectrum with three peaks in the blue, green and red ranges of the spectrum, which is protected by a second semitransparent electrode (top electrode) 466, and by one or more encapsulation layers (not shown in the drawings) in order to protect the device. Such a device is schematically shown in
[0167] The result is thus a device with three groups of pixels 467a, 467b, 467c, each pixel group being characterized by an optical cavity having a different optical thickness, designated as d.sub.R, d.sub.G and d.sub.B respectively. The cavities are formed between the electrode 452 of the pixel that is reflective, and the semitransparent and semi-reflective electrode 466 at the top. The thicknesses d.sub.R, d.sub.G and d.sub.B as well as the position of maximum intensity of the emitting layer, z.sub.w, are chosen so as to form for the group of pixels B 467c a cavity that allows to extract, from the light generated by the OLED stack, which can be a white light, a maximum of blue light in the direction of the normal, for the group of pixels G 467b a maximum of green light, and for the group of pixels R 467a a maximum of red light.
[0168] It is noted that in this drawing, the parameter z.sub.w refers to a white emission that results from the emission emanating from the light-emitting layers having a blue 5712, green 5710 and red 5711 color. For each of these three layers, the position of maximum intensity of the emitting layer can be defined, designated below by the parameters z.sub.B, z.sub.G and z.sub.R, respectively; these parameters are not shown in
[0169] It is also possible to generate the white emission with a combination of a blue emitter and a yellow emitter (not shown in the drawings).
[0170] It is also possible to use an OLED structure of the tandem type, either with a cell emitting blue light B and a cell emitting yellow light Y, or with a cell emitting light B and a cell emitting red and green light RG. The first alternative is illustrated in
[0171] In the tandem cell of
[0172] The second stack 5702 has the same functional structure, with the layers of the succession of layers 576 HIL, HTL, EBL, an emissive layer 578 with an emission color (yellow) different than that of the stack 5701, and the succession of layers 579 HIL, ETL, HBL. The semi-reflective and conductive layer 566, common to all the pixels, forms both the upper reflector of the optical cavity and the common upper electrode of the device.
[0173] The tandem cell of
[0174] The order of the cells B and Y or B and RG can also be inverted with respect to that which is shown in these drawings. The thicknesses d.sub.R, d.sub.G and d.sub.B, as well as the position of maximum intensity of the emitting layers, z.sub.y and z.sub.B or z.sub.RG and z.sub.B, can be optimized in order to obtain a maximum emission at the normal for the three groups of pixels.
[0175] As already explained above, the optical thicknesses d.sub.l, I=R, G, B are defined as the sum of the thicknesses e multiplied by the optical index n of all the layers that are located between the upper surface of the electrode 452/552 and the lower surface of the electrode 466/566. For example, with respect to
[0176] In these equations the index of each parameter refers to the numerical reference used in
[0177] In the same way, the optical position of the emission z.sub.i, J=Y, R, G, RG, W is defined as the sum of the thicknesses e multiplied by the optical index n of all the layers that are located between the position of maximum intensity of emission of the corresponding emitting layer and the lower surface of the electrode 466/566. For example with respect to
[0178] In these equations the index of each parameter refers to the numerical reference used in
[0179] Tables 1 to 3 show the result of an optimization of the main parameters for various configurations. This optimization is aimed at the best optoelectronic performance, in particular a compromise between emission, efficiency and CIE emission spectrum, to determine the key parameters of the device, namely the thicknesses d.sub.R, d.sub.G, and d.sub.B and the position of maximum intensity of the emitting layers z.sub.w (white light for the geometry of
TABLE-US-00001 Geometry of
TABLE-US-00002 Geometry of
TABLE-US-00003 Geometry of
[0180] Thus, according to a first specific embodiment that lends itself in particular to microdisplays, the optoelectronic device according to the invention has at least three groups of pixels, which are, respectively, pixels R (red), G (green) and B (blue), the pixels of each group having an emitting layer (or a photosensitive layer in the case in which said device is a photodetector), which emits (or detects) in the red, green or blue spectrum, respectively, with an optical thickness d.sub.B between approximately 110 nm and approximately 160 nm, an optical thickness d.sub.G between approximately 160 nm and approximately 220 nm, an optical thickness d.sub.R between approximately 190 nm and approximately 240 nm, a parameter designating the optical position of maximum intensity of white light z.sub.w between approximately 50 nm and approximately 130 nm (preferably between approximately 60 nm and approximately 115 nm), a parameter designating the optical position of maximum intensity of blue light z.sub.s between approximately 40 nm and approximately 100 nm (preferably between approximately 45 nm and approximately 90 nm), a parameter designating the optical position of maximum intensity of green light z.sub.G between approximately 60 nm and approximately 130 nm (preferably between approximately 65 nm and approximately 120 nm), and a parameter designating the optical position of maximum intensity of red light z.sub.R between approximately 65 nm and approximately 140 nm (preferably between approximately 70 nm and approximately 130 nm).
[0181] In an advantageous alternative of this embodiment, the optical thickness d.sub.B is between approximately 120 nm and approximately 155 nm, the optical thickness d.sub.G is between approximately 175 nm and approximately 215 nm, the optical thickness d.sub.R is between approximately 195 nm and approximately 230 nm, the parameter z.sub.w is between approximately 60 nm and approximately 115 nm (preferably between approximately 75 nm and approximately 100 nm), the parameter z.sub.B is between approximately 45 nm and approximately 90 nm (preferably between approximately 55 nm and approximately 80 nm), the parameter z.sub.G is between approximately 65 nm and approximately 120 nm (preferably between approximately 70 nm and approximately 110 nm), and the parameter z.sub.R is between approximately 70 nm and approximately 130 nm (preferably between approximately 80 nm and approximately 120 nm).
[0182] According to a second specific embodiment that lends itself in particular to microdisplays, the optoelectronic device according to the invention has at least three groups of pixels, which are, respectively, pixels R (red), G (green) and B (blue), the pixels of each group having a structure of the tandem type in which the bottom cell has an emitting layer (or a photosensitive layer) which emits (or detects) in the blue spectrum, and the top cell has an emitting layer (or a photosensitive layer) which emits (or detects) in the yellow or red and green spectrum, with an optical thickness d.sub.B between approximately 110 nm and approximately 160 nm (preferably between approximately 120 nm and approximately 155 nm), an optical thickness d.sub.G between approximately 160 nm and approximately 220 nm (preferably between approximately 175 nm and approximately 215 nm), an optical thickness d.sub.R between approximately 190 nm and approximately 240 nm (preferably between approximately 195 nm and approximately 230 nm), a parameter designating the optical position of maximum intensity of blue light z.sub.g between approximately 40 nm and approximately 90 nm (preferably between approximately 45 nm and approximately 85 nm), and a parameter designating the optical position of maximum intensity of yellow (or red and green) light z.sub.Y between approximately 60 nm and approximately 140 nm (preferably between approximately 65 nm and approximately 130 nm).
[0183] In an advantageous alternative of this embodiment, the optical thickness d.sub.B is between approximately 120 nm and approximately 155 nm, the optical thickness d.sub.G is between approximately 175 nm and approximately 215 nm, the optical thickness d.sub.R is between approximately 195 nm and approximately 230 nm, the parameter z.sub.B is between approximately 45 nm and approximately 85 nm (preferably between approximately 55 nm and approximately 80 nm), and the parameter z.sub.Y is between approximately 65 nm and approximately 130 nm (preferably between approximately 80 nm and approximately 115 nm).
[0184] According to a third specific embodiment that lends itself in particular to microdisplays, the optoelectronic device according to the invention has at least three groups of pixels, which are, respectively, pixels R (red), G (green) and B (blue), the pixels of each group having a structure of the tandem type in which the bottom cell has an emitting layer (or a photosensitive layer) which emits (or detects) in the blue spectrum, and the top cell has an emitting layer (or a photosensitive layer) which emits (or detects) in the yellow or red and green spectrum, with an optical thickness d.sub.B between approximately 320 nm and approximately 390 nm (preferably between approximately 330 nm and approximately 375 nm), an optical thickness d.sub.G between approximately 425 nm and approximately 500 nm (preferably between approximately 450 nm and approximately 490 nm), an optical thickness d.sub.R between approximately 500 nm and approximately 575 nm (preferably between approximately 510 nm and approximately 565 nm), a parameter designating the optical position of maximum intensity of blue light z.sub.g between approximately 45 nm and approximately 100 nm (preferably between approximately 50 nm and approximately 95 nm), and a parameter designating the optical position of maximum intensity of yellow (or red and green) light z.sub.Y between approximately 120 nm and approximately 390 nm (preferably between approximately 130 nm and approximately 375 nm).
[0185] In an advantageous alternative of this embodiment, the optical thickness d.sub.B is between approximately 335 nm and approximately 375 nm, an optical thickness d.sub.G between approximately 450 nm and approximately 490 nm, an optical thickness d.sub.R between approximately 510 nm and approximately 565 nm, a parameter z.sub.B between approximately 55 nm and approximately 90 nm (preferably between approximately 60 nm and approximately 85 nm), and a parameter z.sub.Y between approximately 130 nm and approximately 375 nm (preferably between approximately 135 nm and approximately 370 nm).
[0186] In relation to
[0187] The starting point is the intermediate product schematically shown in
[0188] Then a second layer 7562 of soft TCO is deposited on the entire structure, as illustrated in
[0189] Then a second layer 7602 of hard TCO is deposited on the entire structure, to arrive at the structure illustrated in
[0190] Then the layer of photosensitive resin 7620 is removed by a wet stripping method and the structure illustrated in
[0191] This device can be used to create a display screen with three primary colors, for example red (R), green (G) and blue (B), in order to create a color screen of the type known by the name “full color”, as described above.
[0192] The invention can be carried out in various other alternatives.
[0193] A first alternative is illustrated in
[0194]
[0195] In a second alternative, which is compatible with all the other alternatives and all the embodiments described here, suitable colored filters 695a, 695b, 695c are added. This is schematically illustrated in
[0196] In the example of
[0197] It is very advantageous to provide an encapsulation system (not shown in the drawings) on the upper electrode 166, 266, 366, 466. It comprises at least one layer, and preferably several layers. It comprises a first layer of alumina, deposited by a conformal deposition technique which is preferably the technique called atomic layer deposition (ALD). It can comprise a second layer of polymer. It can comprise a third layer of alumina, also by ALD. This sequence of alternating layers of alumina and of polymer can be repeated one or more times, the last layer preferably being a layer of alumina or of titanium oxide. Such an encapsulation system protects the device against humidity and oxygen, which would risk degrading some of the layers, and in particular the layers that are part of the organic stack.
[0198] As indicated above, the optoelectronic device according to the invention can be made in the form of a light-emitting device of the OLED type; this can be a microdisplay. The better luminosity obtained according to the invention engenders a reduced electricity consumption and a longer service life. Such a high-luminance microdisplay can be used for example in glasses of the augmented-reality type or in devices of the HUD (Head-Up Display) type. It is advantageously made with at least three groups of pixels of a different color.
[0199] The optoelectronic device according to the invention can also be made as a multispectral optical sensor, containing organic photodiodes. Such a sensor transforms the incident light into an electric signal, which is generated by a photoactive stack of layers, which are preferably organic layers. In one embodiment (not shown in the drawings), this photoactive stack of layers comprises at least a first material, which is an electron donor, and a second material, which is an electron acceptor. According to the choice of the materials and the optical length of the cavities such a sensor can be made to respond in various ranges of the light spectrum, for example in the visible range and/or in the near-infrared range.
[0200] Such a sensor is useful in particular in the spectral range of the near infrared, which typically extends between approximately 780 nm and approximately 10 .Math.m. To create such a sensor, said materials are characterized by the fact that the difference between the energy of the highest occupied level (HOMO - Highest Occupied Molecular Orbital) of said first material and the energy of the lowest unoccupied level (LUMO -Lowest Unoccupied Molecular Orbital) of said second material is less than approximately 1.6 eV.
[0201] Said first material can for example be a phthalocyanine (such as phthalocyanine of zinc or of iron) or an aromatic amine (such as N,N,N′,N′-Tetrakis(4-methoxyphenyl)benzidine, abbreviated MeO-TPD, CAS n° 122738-21-0) or a polythiophene (such as poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene], abbreviated PBTTT, CAS n° 888491-19-8). These materials can be deposited under vacuum. Said second material can be a fullerene, such as C60; these materials can also be deposited under vacuum.
[0202] Such an optoelectronic device can be made in the form of a spectrometer (by providing a plurality of groups of pixels, each group of which has an optical cavity of a different length), and/or in the form of a camera with a spatial and spectral resolution, by providing a plurality of pixels each consisting of a plurality of groups of pixels with an optical cavity of a different length.
LIST OF REFERENCE SYMBOLS
[0203] The following reference signs are used in the drawings and in the description:
TABLE-US-00004 10 Substrate (typically of the CMOS type) 11 Insulant (silicon nitride and/or oxide) 12 Lower electrode 13 First (lower) layer of titanium nitride (TiN) 14 Layer of aluminum 15 Second (upper) layer of titanium nitride (TiN) 16 First layer of TCO 17 First layer of photosensitive resin 18 Second layer of TCO 19 Second layer of photosensitive resin 20 Third layer of TCO 21 Third layer of photosensitive resin 22 Filling photosensitive resin (gap fill) 23 OLED stack 24 Semitransparent common electrode 25 Pixel 26 Pixel 27 Pixel 150 Substrate (typically of the CMOS type, including circuits for controlling the pixels, in the case of an OLED device, or for reading in the case of a sensor device 151 Insulant (typically silicon nitride and/or oxide) 152 Lower electrode 153 Metal layer of 152 154 Second (upper) layer of titanium nitride 152 155 First (lower) layer of titanium nitride 152 156 First layer of TCO (“soft” TCO) 157 Layers of TCO 156, 160 forming an optical spacer 158 Photosensitive resin (photoresist) 160 Second layer of TCO (“hard” TCO) 162 Photosensitive resin (photoresist) 164 Element for filling between pixels (gap-fill) 166 Upper electrode 167 Pixel 168 Group of pixels 170 OLED stack 171 First assembly of 170 175 Second assembly of 170 179 Third assembly of 170 257 Layers of TCO 156, 160 forming an optical spacer 266 Upper electrode 270 OLED stack 271 First assembly of layers of 270 272 Second assembly of layers of 270 273 Third assembly of layers of 270 276 First assembly of layers of 270 278 Second assembly of layers of 270 279 Third assembly of layers of 270 350 Substrate (typically of the CMOS type, including circuits for controlling the pixels, in the case of an OLED device, or for reading in the case of a sensor device 351 Insulant (typically silicon nitride and/or oxide) 352 Lower electrode 360 Second layer of TCO (“hard” TCO) 362 Photosensitive resin (photoresist) 364 Element for filling between pixels (gap-fill) 366 Upper electrode 367 Pixel 370 OLED stack 450 Substrate (typically of the CMOS type, including circuits for controlling the pixels, in the case of an OLED device, or for reading in the case of a sensor device 451 Insulant (typically silicon nitride and/or oxide) 452 Lower electrode 456 First layer of TCO (“soft” TCO) 460 Second layer of TCO (“hard” TCO) 466 Upper electrode 467 Pixel 470 OLED stack 550 Substrate (typically of the CMOS type, including circuits for controlling the pixels, in the case of an OLED device, or for reading in the case of a sensor device 551 Insulant (typically silicon nitride and/or oxide) 552 Lower electrode 560 Second layer of TCO (“hard” TCO) 567 Pixel 570 Tandem OLED stack 571 First assembly of layers of 570 572 Emitting layers of an OLED stack 574 Charge generation layer 575 Second assembly of layer 570 579 Third assembly of layers of 570 680 “Base” layer of TCO (hard) 690 Smoothing layer 695 Color filter 750 Substrate (typically of the CMOS type, including circuits for controlling the pixels, in the case of an OLED device, or for reading in the case of a sensor device 751 Insulant (typically silicon nitride and/or oxide) 752 Lower electrode 762 Photosensitive resin (photoresist) 764 Element for filling between pixels (gap-fill) 767 Pixel 1680 Group of pixels 1700 OLED stack 1751 Emitting layers of an OLED stack 1752 Emitting layers of an OLED stack 2701 1.sup.st assembly of a tandem OLED stack 2702 2.sup.nd assembly of a tandem OLED stack 3561 First layer of TCO (soft) 3562 First layer of TCO (soft) 3601 Second layer of TCO (hard) 3602 Second layer of TCO (hard) 3620 Photosensitive resin (photoresist) 4561 First layer of TCO (soft) 4562 First layer of TCO (soft) 4601 Second layer of TCO (hard) 4602 Second layer of TCO (hard) 5561 First layer of TCO (soft) 5562 First layer of TCO (soft) 5601 Second layer of TCO (hard) 5602 Second layer of TCO (hard) 5701 1.sup.st stack of layers of a tandem OLED stack 570 5702 2.sup.nd stack of layers of a tandem OLED stack 570 5710 Emitting layers of an OLED stack 5711 Emitting layers of an OLED stack 5712 Emitting layers of an OLED stack 5781 1.sup.st emissive layer of an OLED stack 5782 2.sup.nd emissive layer of an OLED stack 7561 First layer of TCO (soft) 7562 First layer of TCO (soft) 7601 Second layer of TCO (hard) 7602 Second layer of TCO (hard) 7620 Photosensitive resin (photoresist)