DATA RECORDING ON CERAMIC MATERIAL

Description

[0001] The present invention relates to a method for recording data in a layer of a ceramic material.

[0002] US 2015 / 0302926 A1 discloses a recording technique in which a plurality of light spots are simultaneously formed by using an ultra-short pulse laser and a spatial phase modulator, and a plurality of recording dots having refractive indexes different from those of the vicinities thereof are formed inside a recording medium. US 5,761,111 B1 relates to sub-micron-scale, micron-scale and greater than micron-scale, crack-free and regularly-shaped structures of high-contrast refractive index provided in transparent storage media by controllably focusing ultrashort laser pulses in the bulk of virtually any transparent medium.

[0003] The applicant of the present invention has developed a method for long-term storage of information and a storage medium therefor (see PCT / EP2019 / 071805 and PCT / EP2020 / 068892). According to one aspect of said method for long-term storage of information, information is encoded on a writable plate comprising a ceramic material by using a laser beam to manipulate localized areas of the writable plate. While this method can, in principle, be performed with a laser beam having a fixed focal point by mounting the writable plate on an XY positioning system and moving those localized areas of the writable plate to the laser focus where encoding is to take place, said method is cumbersome and time-consuming.

[0004] It is thus an object of the present invention to provide an improved method for recording data in a layer of a ceramic material, which is suitable for recording a large amount of data in a relatively small amount of time.

[0005] This object is achieved by a method according to claim 1. Preferred embodiments of the present invention are described in the dependent claims.

[0006] Accordingly, the present invention relates to a method for recording data in a layer of a ceramic material. According to said method, a layer of a ceramic material is provided and a plurality of regions of the layer of the ceramic material are selectively illuminated with a laser beam using a digital micromirror device (DMD). The parameters of the laser beam and the time of illumination for each of the selected regions are configured so as to sufficiently manipulate each of the selected regions in order to record data on or in the layer of the ceramic material.

[0007] The DMD comprises an array or a matrix of micromirrors which allow to selectively illuminate predetermined pixels on the ceramic material by adjusting respective micromirrors of the array or matrix. Thus, a huge number of pixels on the ceramic material may be illuminated simultaneously and in a well-controlled manner, which can be easily automatized. Depending on the number of micromirrors present in the DMD, millions of selected regions (i.e. pixels) of the layer of the ceramic material can be manipulated simultaneously during a timespan which is sufficient to manipulate one selected region in order to record data. Such digital micromirror devices are readily available and can be simply implemented into a recording device.

[0008] Manipulation of the selected regions of the layer of the ceramic material by means of laser illumination comprises ablating the respective regions of the layer of the ceramic material. Typically, the laser light will heat the impact areas of the laser beam which, in turn, may cause ablation of the material within or close to the impact areas. According to the invention, an ultra-short pulse laser such as a picosecond laser or a femtosecond laser is used. Thus, so-called Coulomb explosions lead to material ablation at higher energy densities. Dependent on the polarisation of the beam such Coulomb explosions may create recordable oval shaped recesses or holes with the long and short axes of the oval being dependent again on the polarisation of the beam.

[0009] Accordingly, the recorded data may be encoded in the layer of the ceramic material by creating recessions or holes in the material. Recesses or holes of different depths may be created, wherein each depth corresponds to a predefined bit of information as described in PCT / EP2020 / 068892. For this purpose, the layer of the ceramic material may be illuminated with two or more laser pulses, wherein the micromirrors of the DMD are adjusted between subsequent pulses so as to achieve regions of the layer of the ceramic material which are (i) never illuminated, (ii) illuminated once with a single laser pulse, (iii) illuminated twice with two laser pulses and so on.

[0010] It has been shown in experiments before by the applicant that a layer of CrN with a thickness of 5 µm can be visibly and reliably manipulated by a single femtosecond laser pulse (see PCT / EP2020 / 068892). Accordingly, the method of the present invention allows for encoding at least several thousands and up to a couple of millions pixels within several hundred femtoseconds. Thus, the recording speed of the inventive method is merely limited by the number of micromirrors of the DMD and the time required to adjust the micromirrors.

[0011] Preferably, the layer of the ceramic material is moved laterally or translated during recording, e.g. by means of an XY positioning system (with the z axis being perpendicular to the surface of the layer) such as a scanning stage. Thus, once an array or matrix of pixels has been recorded, an adjacent array or matrix of pixels may be recorded by simply moving the layer of the ceramic material to an adjacent area.

[0012] Accordingly, the inventive method preferably comprises the steps of selectively illuminating a plurality of regions within a first area of the layer of the ceramic material with the laser beam using the DMD, wherein the first area can be covered by the DMD; translating the layer of the ceramic material so that a second area different from the first area can be covered by the DMD; and selectively illuminating a plurality of regions within the second area of the layer of the ceramic material with the laser beam using the DMD.

[0013] If both the DMD and the XY positioning system are properly controlled, data recording speeds of at least 10 MB / s, preferably at least 100 MB / s, preferably at least 1 GB / s, and more preferably at least 10 GB / s can be achieved.

[0014] Preferably, the laser beam (i.e., the multiple laser beams emitted from the DMD) is focused onto the layer of the ceramic material by means of a lens (or more complex optics) having a high numerical aperture preferably a numerical aperture of at least 0.5, more preferably of at least 0.8. Preferably, immersion optics are used in order to further increase the numerical aperture. If immersion optics are being used the numerical aperture may be at least 1.0, preferably at least 1.2.

[0015] It is further preferred to utilize a beam shaping device to create certain beam shapes that are advantageous for data recording. For example, a matrix of laser zone plates may be transmitted by the multiple laser beams originating from the DMD. These laser zone plates may, for example, be adapted to create a needle-like Bessel beam for each of the multiple laser beams.

[0016] A Bessel beam has the advantage of a substantially increased depth of focus. While the focus length of a regular Gaussian beam is in the order of the wavelength of the focused light, the focus length which can be achieved with a Bessel beam amounts to at least 4 times the wavelength of the focus light. At the same time, the width of the focus is about one half of the focus width which can be achieved by a Gaussian beam.

[0017] In general, the size of the features which can be achieved by the inventive method (e.g. the diameter of a recess in the ceramic material) varies between 2 / 3 λ (air) and 1 / 2 λ (immersion) for a Gaussian beam and between 1 / 3 λ (air) and 1 / 4 λ (immersion) for a Bessel beam (where λ is the wavelength of the laser light). Thus, the Bessel beam shape is advantageous in that smaller process features and, accordingly, a larger recorded data density can be achieved. Moreover, the increased focal length of the Bessel beam is advantageous in that, for example, deeper recesses may be generated. This is, in particular, of relevance if features of different depths are to be generated in order to encode information by means of, e.g., the depth of a recess. Since the focus of a Gaussian beam is cone-shaped, increasing the depth of a recess implies enhancing the diameter of the recess at the surface. By contrast, the more cylindrical focus of a Bessel beam allows for creating much deeper recesses with almost constant diameter.

[0018] Such Bessel beams may also be generated by means of other beam shaping devices. One particularly preferred example of a beam shaping device is a spatial light modulator, which is particularly versatile because it can be utilized to create Bessel beams, to allow for optical proximity control and to provide a phase-shift mask.

[0019] The layer of the ceramic material comprises a metal nitride such as CrN, CrAlN, TiN, TiCN, TiAlN, ZrN, AlN, VN, Si 3 N 4 , ThN, HfN, BN; and / or a metal carbide such as TiC, CrC, Al 4 C 3 , VC, ZrC, HfC, ThC, B 4 C, SiC; and / or a metal oxide such as Al 2 O 3 , TiO 2 , SiO 2 , ZrO 2 , ThO 2 , MgO, Cr 2 O 3 , Zr 2 O 3 , V 2 O 3 ; and / or a metal boride such as TiB 2 , ZrB 2 , CrB 2 , VB 2 , SiB 6 , ThB 2 , HfB 2 , WB 2, WB 4 ; and / or a metal silicide such as TiSi 2 , ZrSi 2 , MoSi 2 , WSi 2 , PtSi, Mg 2 Si. Particular preferred materials are B 4 C, HfC, Cr 2 O 3 , ZrB 2 , CrB 2 , SiB 6 , Si 3 N 4 , ThN, CrN and CrAlN. These materials provide sufficient hardness and resistance to environmental degradation for long term storage of the recorded data.

[0020] The step of providing a layer of a ceramic material comprises providing a substrate and coating the substrate with the layer of the ceramic material different from the material of the ceramic substrate. Thus, only a small amount of the possibly more expensive coating material is needed while structural integrity is achieved with a robust and potentially cheaper substrate. The layer of the ceramic material has a thickness no greater than 10 µm, preferably no greater than 5 µm, more preferably no greater than 2 µm, more preferably no greater than 1 µm, even more preferably no greater than 100 nm and most preferably no greater than 10 nm.

[0021] Furthermore, the use of a substrate may allow for generating optical contrast between the substrate (where a hole is generated in the coating) and the surrounding coating material. Preferably, the manipulation of the selected areas causes these areas to become distinguishable from the surrounding material. For some applications, this may comprise to achieve optical distinguishability. However, in other instances (in particular, if the encoded structures are too small) these areas may only be distinguished from the surrounding material by means of, e.g., a scanning electron microscope or measurement of another physical parameter change for example of magnetic, dielectric or conductive properties.

[0022] Preferably, the ceramic substrate comprises an oxidic ceramic, more preferably the ceramic substrate comprises at least 90%, most preferably at least 95%, by weight of one or a combination of: Al 2 O 3 , TiO 2 , SiO 2 , ZrO 2 , ThO 2 , MgO, Cr 2 O 3 , Zr 2 O 3 , V 2 O 3 . These materials are known to be particularly durable under various circumstances and / or to resist environmental degradation. Thus, these materials are particularly suitable for long-term storage under different conditions. It is particularly preferred that the ceramic substrate comprises one or a combination of: Al 2 O 3 , ZrO 2 , Zr(SiO 4 ), SiO 2 , and MgO.

[0023] Preferably, the ceramic substrate comprises a non-oxidic ceramic, more preferably the ceramic substrate comprises at least 90%, most preferably at least 95%, by weight of one or a combination of: a metal nitride such as CrN, CrAlN, TiN, TiCN, TiAlN, ZrN, AlN, VN, Si 3 N 4 , ThN, HfN, BN; a metal carbide such as TiC, CrC, Al 4 C 3 , VC, ZrC, HfC, ThC, B 4 C, SiC; a metal boride such as TiB 2 , ZrB 2 , CrB 2 , VB 2, , SiB 6 ,ThB 2 , HfB 2 , WB 2 , WB 4 ; and a metal silicide such as TiSi 2 , ZrSi 2 , MoSi 2 , WSi 2 , PtSi, Mg 2 Si. These materials are known to be particularly durable under various circumstances and / or to resist environmental degradation. Thus, these materials are particularly suitable for long-term storage under different conditions. It is particularly preferred that the ceramic substrate comprises one or a combination of: BN, CrSi 2 , SiC, and SiB 6 .

[0024] Preferably, the ceramic substrate comprises one or a combination of Ni, Cr, Co, Fe, W, Mo or other metals with a melting point above 1,400 °C. Preferably, the ceramic material and the metal form a metal matrix composite with the ceramic material being dispersed in the metal or metal alloy. Preferably, the metal amounts to 5-30 % by weight, preferably 10-20 % by weight of the ceramic substrate, i.e. the metal matrix composite. Particularly preferred metal matrix composites are: WC / Co-Ni-Mo, BN / Co-Ni-Mo, TiN / Co-Ni-Mo and / or SiC / Co-Ni-Mo.

[0025] The layer of the ceramic material is coated directly onto the ceramic substrate, i.e. without any intermediate layer being present, so as to achieve a strong bond between the ceramic substrate and the layer of the ceramic material. The coated ceramic substrate is tempered before and / or after recording in order to achieve such strong bonding. Tempering generates a sintered interface between the ceramic substrate and the layer of the ceramic material. The sintered interface may comprise at least one element from both the substrate material and the ceramic material because one or more elements from one of the two adjacent layers may diffuse into the other layer of the two adjacent layers. The presence of the sintered interface may further strengthen the bond between the ceramic substrate and the layer of the ceramic material.

[0026] Preferably tempering the coated ceramic substrate involves heating the coated ceramic substrate to a temperature within a range of 200 °C to 4,000 °C, more preferably within a range of 1,000 °C to 2,000 °C. The tempering process may comprise a heating phase with a temperature increase of at least 10 K per hour, a plateau phase at a peak temperature for at least 1 minute and finally a cooling phase with a temperature decrease of at least 10 K per hour. The tempering process may assist in hardening the ceramic substrate and / or permanently bonding the ceramic material to the ceramic substrate.

[0027] Preferably the selected regions of the layer of ceramic material are heated to at least a melting temperature of the ceramic material such that the selected regions of the layer of ceramic material are heated to a temperature of at least 3,000 °C, even more preferably at least 3,200 °C, most preferably at least 3,500 °C, most preferably at least 4,000 °C. Laser ablation of selected regions of the layer of ceramic material may reveal the underlying ceramic substrate leading to a (optically) distinguishable contrast of the manipulated area relative to the rest of the layer of ceramic material.

[0028] According to a particularly preferred embodiment of the present invention, the substrate is transparent to the wavelength of the laser beam. Preferably, the substrate has a transmission of at least 95%, more preferably of at least 97% and most preferably of at least 99% for light having the wavelength of the laser beam. The substrate may, for example, comprise a glassy transparent ceramic material or a crystalline ceramic material. A particularly suitable crystalline ceramic material is sapphire (Al 2 O 3 ), silica (SiO 2 ), zirconium (Zr(SiO 4 )), ZrO 2 , MgO.

[0029] Such a transparent material is particularly advantageous as it allows for selectively illuminating a plurality of regions of the layer of the ceramic material (coated onto the substrate) through the transparent substrate. Thus, any debris generated during recording is generated on a surface of the coated substrate opposite to the recording optics. Accordingly, said surface may be easily cleaned and / or cooled without affecting the recording optics.

[0030] Due to the high transmission factor of the transparent substrate material, the laser light does not interact with the substrate and simply passes therethrough in order to, e.g., ablate the coating only. In particular, the substrate material is not substantially heated by the laser beam.

[0031] Preferably, the laser beam (i.e., each of the multiple laser beams emitted from the DMD) has a minimum focal diameter no greater than 400 nm, more preferably no greater than 300 nm, even more preferably no greater than 200 nm, and most preferably no greater than 100 nm.

[0032] The present disclosure further relates to a device for recording data on or in a layer of a ceramic material, which may be utilized in the context of the inventive method. The device, which is not covered by the claimed invention, comprises a laser source, a digital micromirror device (DMD) adapted to emit multiple laser beams, collimating optics for collimating laser light emitted by the laser source onto the DMD, a substrate holder for mounting a substrate, and focusing optics adapted for focusing each of the multiple laser beams emitted by the DMD onto a substrate mounted on the substrate holder. The power density of each of the multiple laser beams emitted by the DMD is greater than 100 mJ / cm 2< , preferably greater than 400 mJ / cm 2< , more preferably greater than 800 mJ / cm 2< , most preferably greater than 1 J / cm 2< .

[0033] The power density of the laser beams is preferably adapted to manipulate a layer of a ceramic material sufficiently in order to record data on or in the layer of the ceramic material. Preferably, the power density of the laser beams allows for ablating the above-mentioned ceramic materials.

[0034] The focusing optics preferably comprises a lens (or more complex optics) having a high numerical aperture, preferably a numerical aperture of at least 0.5, more preferably of at least 0.8. If immersion optics are being used the numerical aperture may be at least 1.0, more preferably at least 1.2.

[0035] The device preferably further comprises a beam shaping device, preferably a matrix of laser zone plates or a spatial light modulator in order to create, e.g., a plurality of Bessel beams as discussed above. Such beam shaping device is preferably positioned before the focusing optics. In this case, preferably a plurality of lenses, preferably Fresnel lenses, are located directly behind the beam shaping device in order to focus, e.g., the Bessel beams.

[0036] At the substrate, each of the multiple laser beams preferably is a Bessel beam. At the substrate, each of the multiple laser beams preferably has a minimum focal diameter no greater than 400 nm, more preferably no greater than 300 nm, even more preferably no greater than 200 nm and most preferably no greater than 100 nm.

[0037] The substrate holder is preferably mounted on an XY positioning system such as a scanning stage. The device preferably comprises a processor configured for controlling the DMD and the XY positioning system so as to sequentially illuminate adjacent areas or pixel arrays of the substrate mounted on the substrate holder.

[0038] This processor (or an additional processing unit) is preferably adapted and configured to receive a set of data to be recorded (i.e., analogue or digital data such as text, numbers, an array of pixels, a QR code, or the like) and to control the components of the device (in particular, the DMD and the XY positioning system and optionally the beam shaping device) to perform the inventive method so as to record the received set of data on or in the layer of ceramic material.

[0039] Preferred embodiments of the present invention will be further elucidated with reference to the figures, which show: Fig. 1a schematic view of a device for recording data; Fig. 2schematically different recording alternatives; Fig. 3schematically a device for recording data; and Fig. 4a schematic view of a combination of a polarizer, a zone plate and a lens as well as a graph of the resulting beam shape and focal length along the axis of the laser beam.

[0040] Fig. 1 shows a schematic illustration of a device for recording data on or in a layer of a ceramic material. The device comprises a laser source 2 emitting laser light onto a DMD 3 comprising multiple micromirrors 3a arranged in an array. The DMD 3 is adapted to emit multiple laser beams 4 along either a first direction (i.e., for recording) or along a second direction (indicated with reference numeral 9) for each micromirror being in an "off" state diverting those laser beams 9 into a beam dump (not shown). Usually, the device will further comprise collimating optics (not shown in Fig. 1) for collimating laser light emitted by the laser source 2 onto the DMD 3. The device further comprises a substrate holder (not shown in Fig. 1) for mounting a substrate 7 and focusing optics 8 adapted for focusing each of the multiple laser beams 4 emitted by the DMD onto a substrate 7 mounted on the substrate holder. The focusing optics 8 may, for example, comprise standard microscope optics having a high numerical aperture.

[0041] In the example shown in Fig. 1, the substrate 7 comprises a ceramic coating or a layer of a ceramic material 1 which is locally ablated by means of the focused laser beams 4. In Fig. 1, the ceramic coating 1 is provided on top of the substrate 7 (see also top figure in Fig. 2). Alternatively, the ceramic coating may be provided on a bottom or back side of the substrate 7 as shown in the bottom figure of Fig. 2. Since the laser beams 4 in this case have to pass through the substrate 7, the material of the substrate 7 need be transparent for the wavelength of the laser light in this case.

[0042] This is particularly preferred because any debris generated during ablation will be separated from the focusing optics 8 by means of the substrate 7. Thus, the focusing optics 8 will not be negatively affected by said debris and it is much easier to clean the surface of the ceramic coating 1 immediately after or even during recording.

[0043] Preferably, the thickness of the substrate is adapted to the focussing optics of the device being used. For example, the thickness of the substrate should be smaller than the focal length of the focussing optics in order to reach the ceramic coating.

[0044] Moreover, the arrangement shown in the bottom of Fig. 2 does also allow for cooling the ceramic coating 1 during ablation, for example by letting a cooling fluid flow along said ceramic coating 1. This will improve accuracy of the ablation process because heat transfer from the laser focus to surrounding areas may be eliminated. For example, a cross jet of air (e.g., an air blade) or a liquid such as water or other immersion liquids may be provided for this purpose. Said cross jet may, in addition, drain off the debris generated during ablation.

[0045] Such a cross jet may also be provided in case of the arrangement shown in the top figure of Fig. 2. However, said cross jet in this example has to be designed so as not to interfere with the optics. For example, if immersion optics is used the immersion liquid may be provided in a cross flow which is preferably laminar in order to avoid any optical effects due to turbulences within the immersion liquid.

[0046] Some more details of another exemplary device are shown in Fig. 3. For example, Fig. 3 shows the collimating optics 5 for collimating laser light emitted by the laser source 2 onto the DMD 3 as well as further optical components such as a spatial filter 10, 11. The substrate holder 6 is, in case of Fig. 3, a XY positioning system for translating the substrate 7 along the x-y-plane (with z being perpendicular to the surface of the substrate 7). Both the DMD 3 and the XY positioning system 6 are controlled by a computer 13 which is configured to control the DMD 3 and the XY positioning system 6 so as to perform the following steps: selectively illuminating a plurality of regions within a first area of the layer 1 of the ceramic material with the laser beam using the DMD 3, wherein the first area can be covered by the DMD 3; translating the layer 1 of the ceramic material (i.e., the entire substrate 7 in the present case) so that a second area different from the first area can be covered by the DMD 3; and selectively illuminating a plurality of regions within the second area of the layer 1 of the ceramic material with the laser beam using the DMD 3.

[0047] As discussed previously, the device preferably comprises a beam shaping device to achieve, e.g., Bessel beams. For example, a matrix of laser zone plates 12 may be provided between the DMD 3 and the focusing optics 8 so as to shape each of the laser beams 4 (see Fig. 1) into a Bessel beam shape. Each Bessel beam is then focussed onto the substrate 7 by means of an attributed Fresnel lens 8. In order to properly illuminate the matrix of laser zone plates 12 additional collimating optics 14a and 14b may be provided. This principle is further elucidated in Fig. 4 which shows (for a single beamlet) how a Bessel beam is generated by a combination of an optical element 12a creating circularly polarized light and a binary phase element 12b for creating a Bessel beam which is then focused onto the substrate 7 by means of an attributed high NA lens 8 (or a Fresnel lens 8). As indicated also in Fig. 4, a focus length of at least 4 times the wavelength of the laser light may be achieved by using such a Bessel beam. Moreover, the focus has a much more cylindrical shape than a Gaussian beam.

Claims

1. A method for recording data in a layer of a ceramic material (1), the method comprising the steps of: providing a layer of a ceramic material (1); and selectively illuminating a plurality of regions of the layer of the ceramic material (1) simultaneously with a picosecond laser (2) or a femtosecond laser (2) beam using a digital micromirror device (3), wherein the laser light emitted from the picosecond laser (2) or the femtosecond laser (2) is collimated onto the digital micromirror device (3) by means of collimating optics (5) and wherein the multiple laser beams originating from the digital micromirror device (3) are focused onto the layer of the ceramic material (1) by means of focusing optics (8); wherein the parameters of the laser beam and the time of illumination for each of the selected regions are configured so as to ablate each of the selected regions in order to record data in the layer of the ceramic material (1) by creating recesses or holes in the layer of the ceramic material (1), each recess or hole being open to atmosphere; wherein providing the layer of a ceramic material (1) comprises providing a substrate (7) and coating the substrate (7) with the layer of the ceramic material (1) different from the material of the substrate (7), wherein the layer of the ceramic material (1) is directly coated onto the ceramic substrate (7) and the coated ceramic substrate is tempered before and / or after recording so as to generate a sintered interface between the ceramic substrate (7) and the layer of the ceramic material (1), wherein the layer of the ceramic material (1) has a thickness no greater than 10 µm; and wherein the layer of the ceramic material (1) comprises at least one of: TiC, Al4C3, VC, ZrC, HfC, ThC, B4C, SiC; a metal nitride such as CrN, CrAlN, TiN, TiCN, TiAlN, ZrN, AlN, VN, Si3N4, ThN, HfN, BN; a metal oxide such as Al2O3, TiO2, SiO2, ZrO2, ThO2, MgO, Cr2O3, Zr2O3, V2O3; a metal boride such as TiB2, ZrB2, CrB2, VB2, SiB6,ThB2, HfB2, WB2, WB4; or a metal silicide such as TiSi2, ZrSi2, MoSi2, WSi2, PtSi, Mg2Si.

2. The method of claim 1, wherein the laser beam is a Bessel beam.

3. The method of any of the preceding claims, wherein the layer of the ceramic material is moved laterally during recording and wherein the method further comprises the steps of: selectively illuminating a plurality of regions within a first area of the layer of the ceramic material with the laser beam using the digital micromirror device, wherein the first area can be covered by the digital micromirror device; translating the layer of the ceramic material so that a second area different from the first area can be covered by the digital micromirror device; and selectively illuminating a plurality of regions within the second area of the layer of the ceramic material with the laser beam using the digital micromirror device.

4. The method of any of the preceding claims, wherein the layer of the ceramic material preferably has a thickness no greater than 5 µm, preferably no greater than 2 µm, more preferably no greater than 1 µm, even more preferably no greater than 100 nm and most preferably no greater than 10 nm.

5. The method of any of the preceding claims, wherein the substrate comprises at least 90%, preferably at least 95%, by weight of one or a combination of: Al2O3, TiO2, SiO2, ZrO2, ThO2, MgO, Cr2O3, Zr2O3, V2O3; and / or wherein the ceramic substrate comprises at least 90%, preferably at least 95%, by weight of one or a combination of: a metal nitride such as CrN, CrAlN, TiN, TiCN, TiAlN, ZrN, AlN, VN, Si3N4, ThN, HfN, BN; a metal carbide such as TiC, CrC, Al4C3, VC, ZrC, HfC, ThC, B4C, SiC; a metal boride such as TiB2, ZrB2, CrB2, VB2, SiB6, ThB2, HfB2, WB2, WB4; and a metal silicide such as TiSi2, ZrSi2, MoSi2, WSi2, PtSi, Mg2Si.

6. The method of any of the preceding claims, wherein the substrate is transparent to the wavelength of the laser beam, wherein preferably the substrate comprises a glassy transparent ceramic material or a crystalline ceramic material and / or wherein the substrate comprises one or a combination of: sapphire (Al2O3), silica (SiO2), zirconium (Zr(SiO4)), ZrO2.

7. The method of claim 6, wherein selectively illuminating a plurality of regions of the layer of the ceramic material with a laser beam using a digital micromirror device comprises illuminating the layer of the ceramic material through the transparent substrate.

8. The method of any of the preceding claims, wherein the laser beam has a minimum focal diameter no greater than 400 nm, preferably no greater than 300 nm, more preferably no greater than 200 nm, even more preferably no greater than 100 nm.