比利时专利BE1021021B1 SPUTTER TARGET OFF (Go) Zn Sn-OXIDE

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专利摘要:
Sputtering target from (Ga) Zn Sn-oxide A sputtering target with a one-piece topcoat comprising a mixture of oxides of zinc, tin and optionally gallium, characterized in that said one-piece topcoat has a length of at least 80 cm; a method for creating such a sputtering target and using such a target to create layers.
公开号:BE1021021B1
申请号:E2014/0062
申请日:2014-02-04
公开日:2014-12-19
发明作者:Berghaus Jörg Oberste；Bosscher Wilmert De
申请人:Soleras Advanced Coatings Bvba；
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专利说明:

Sputtering target from (Ga) Zn Sn-oxide
Technical field of the invention
The present invention relates to the field of sputtering targets from (Ga) Zn Sn oxide for the production of thin semiconductor layers from (Ga) Zn Sn oxide.
BACKGROUND OF THE INVENTION
Popular and established display technologies such as Liquid Crystal Displays and emerging display technologies such as organic LED displays are displays with an active matrix. An active matrix display comprises an array of thin film transistors. Polycrystalline and more recently amorphous silicone is traditionally used as the semiconductor channel layer preferably in active matrix displays. The biggest disadvantage of amorphous silicone is its low mobility of charge carriers (about 1 cm2 / V.s for electrons) which limits the performance of the device. Nowadays, alternatives are proposed that belong to the family of so-called oxide semiconductors. For example, oxides of In (indium) Ga (gallium) Zn (zinc) were produced with a mobility of charge carriers in the range of 10 to 40 cm 2 / V.s. In addition, In Ga Zn oxides enable homogeneous deposition on large surfaces. This makes In Ga Zn-oxides the favorite oxide semiconductor for next-generation active matrix displays. A major disadvantage of In Ga Zn oxides is the fact that In is both toxic and limited in quantity on earth. This is expected to be the first element whose scarcity will curb the growth of future display technologies. That is why there is a need for feasible indium-free alternatives to In Ga Zn oxides. Zn Sn oxides and Zn Sn Ga oxides have been proposed as alternatives, but it is a major challenge to produce them with acceptable quality.
The article "The influence of mechanical activation on zinc stannate spinel formatiori" by N. Nikolic et al. In the Journal of the European Ceramic Society 21 (2001) studies the formation of ceramic zinc stannate during treatments of tablets obtained from ZnO- and Sn02- powder mixtures that are mechanically activated in a high-energy mill, and explains that zinc stannate is preferably formed by a solid state reaction during sintering with an ever-longer duration of high-energy milling. US20070215456A1 describes a sintering process for the manufacture of targets from Zn Sn-oxide and from a sputtering target from Ga Zn Sn-oxide. The process involves prolonged grinding (18 hours) of the raw material, sintering in an oxygen-rich atmosphere for longer than 15 hours, and then a reduction process by heating in a non-oxidative atmosphere for longer than 7 hours to make a single sintered mass. US20070215456A1 illustrates by means of examples that deviation from the preferred procedure can lead to a high frequency of breakdowns on the target surface and insufficient strength of the sintered mass. Insufficient strength can be caused by the lack of the composite phase of the zinc stannate (or low amounts of this phase) in the sintered mass. US20070215456A1 makes no mention of the length of the obtained sputtering target (single sintered mass) but suggests that, if necessary, different pieces of the sintered masses can be arranged in separate parts to make a target with a large area. The resistivity of the targets from Zn Sn oxide was in the range of 2.3 kO.cm to 4.7 kΩ.cm and the resistivity of the target from Zn Sn Ga oxides was 0.11 kΩ.cm. US20070215456A1 indicates that these sputtering targets can be used with a DC load power density of 5.513 W / cm 2. Although these figures are favorable in comparison with the rest of the prior art, there is still room for improvement. Moreover, the sintering method currently used for the manufacture of these sputtering targets is very time-consuming and labor-intensive.
That is why there is a need for new indium-free alternatives for sputtering targets from In Ga Zn oxides, especially for coatings on large surfaces.
Summary of the invention
It is an object of the present invention to provide good sputtering targets and methods of producing them.
It is an advantage of embodiments of the present invention that long (Ga) Zn Sn oxide targets can be produced in one piece. For example, targets from (Ga) Zn Sn oxide can be produced in one piece with a length of 50 cm or more.
It is an advantage of embodiments of the present invention that targets can be produced from (Ga) Zn Sn oxide with a top layer with a low resistivity. For example, in some embodiments, targets from (Ga) Zn Sn oxide can be produced with a resistivity in the top layer of less than 10 µm. In embodiments, this low resistivity can be obtained without the use of expensive reduction processes afterwards and / or without long and expensive grinding of the base powders.
It is an advantage of embodiments of the present invention that targets can be produced from (Ga) Zn Sn oxide that can be used in DC sputtering or in AC sputtering with a frequency of less than 350 kHz.
It is an advantage of embodiments of the present invention that targets of (Ga) Zn Sn oxide can be produced that have a homogeneous top layer.
It is an advantage of embodiments of the present invention that targets of (Ga) Zn Sn oxide can be produced that have a homogeneous top layer consisting essentially of zinc stannate.
It is an advantage of embodiments of the present invention that targets can be produced from (Ga) Zn Sn oxide that can be used in a sputtering process with a high power density without producing a too high frequency of breakdowns. For example, in embodiments, the sputtering process can take place at a power density of at least 10 kW average DC power per meter target length.
It is an advantage of embodiments of the present invention that targets of (Ga) Zn Sn oxide can be produced wherein the top layer can be applied to a support with different shapes. For example, the targets from (Ga) Zn Sn oxide have a flat shape (e.g., circular or rectangular) when formed on a plate or have a more complex shape such as cylindrical when formed on a tube.
In embodiments, the support may be a metal support, for example a metal (support) tube.
It is a still further advantage of embodiments of the present invention that targets of (Ga) Zn Sn oxide can be produced by a relatively simple and inexpensive method, namely thermal spraying.
The above object is achieved by a method and device according to the present invention.
In a first aspect, the present invention relates to a sputtering target with a one-piece top layer comprising a mixture of oxides of zinc, tin and optionally gallium, characterized in that said one-piece top layer has a length of at least 50 cm , preferably at least 65 cm, more preferably at least 80 cm, and even more preferably at least 100 cm. Although it appears that the physical properties of the obtained top layers do not prevent any length of top layer from being obtained, in some embodiments a typical practical upper limit can be set at 4 m, 3 m, 2 m or 1 m. One from one top layer piece, ie a top layer that does not consist of 2 or more pieces (eg sleeves or tiles) that are attached to each other, is very advantageous since this eliminates the preferential sputtering that often occurs at the boundary between top layer pieces. Such sputtering from the edges of the pieces leads to the formation of heterogeneous strips in the sputtered layer. A one-piece top layer therefore enables a homogeneously sputtered layer. Furthermore, excessive breakdown can occur at these interfaces between two adjacent pieces, which has consequences for the quality and performance of the layer.
In an embodiment of the first aspect, the amount of Ga in said mixture of oxides relative to the total amount of Ga, Zn and Sn can be between 0 and 20 at% or between 1 and 20 at%, preferably between 3 and 15 at% , more preferably between 4 and 9 at%. The presence of Ga in the mixture of oxides of the sputtering target is beneficial because it improves electrical performance. Without being limited by theory, it is believed that it suppresses the generation of oxygen vacancies in the sputtered layer, which reduces the concentration of free carriers and the number of electron pin locations that can reduce the electrical performance of the oxide semiconductor transistor. Moreover, it was surprisingly found that a sputtering target with a one-piece top layer comprising a mixture of oxides of zinc, tin and optionally gallium of at least 50 cm could be obtained by a method according to the sixth aspect of the present invention. As far as known to the inventors, it is not possible to obtain such a long top layer comprising a mixture of oxides of zinc, tin and optionally gallium by sintering.
In an embodiment of the first aspect, the amount of Zn in said mixture of oxides relative to the total amount of Ga, Zn and Sn can be between 15 and 85 at%, preferably between 30 and 77 at%.
In an embodiment of the first aspect, the relative amount of Sn is between 15 and 55 at%.
In an embodiment of the first aspect, the amount of Zn in said mixture of oxides relative to the total amount of Ga, Zn and Sn can be between 15 and 85 at%, preferably between 30 and 77 at%, more preferably between 56 and 70 at% and the relative amount of Sn may be between 15 and 55 at%, preferably between 28 and 35 at%. This composition is advantageous because it is more likely that an oxide phase of zinc stannate is formed during thermal spraying, so as to make a strong and homogeneous target. The formation of an amorphous thin layer is also facilitated by sputtering a target of this composition, which leads to good transistor performance.
In embodiments of the first aspect, the mixture of oxides contains zinc stannate oxide.
In an embodiment of the first aspect, the sum of all zinc stannate oxides in mol% that are present in said top layer may be higher than any other oxide present therein. For example, if the top layer also comprises ZnO and SnO2, the sum of all zinc stannate oxides in mole% may be higher than the amount of SnO2 on the one hand and then the amount of ZnO on the other hand. In embodiments, said zinc stannate oxides are mostly (> 50 mole%) Zn 2 SnO 4 - In embodiments, said zinc stannate oxides are essentially (> 90 mole% and preferably> 95 mole%) Zn 2 SnO 4. In embodiments, said zinc stannate oxides are zinc stannate oxide Zn 2 SnO 4. The fact that the sum of all zinc stannate oxides in mol% present in said top layer is higher than any other oxides present therein is advantageous because the inventors could correlate the presence of zinc stannate oxides in the top layer with higher top layer quality. In particular, the mechanical properties are very good so that long sputtering targets can be formed. The density of the sputtering targets is also particularly good.
In an embodiment of the first aspect, the material comprising said one-piece top layer has a resistivity of less than 10 µm, preferably less than 1 µm, more preferably less than 0.1 µm, most preferably less than 3 * 10 '2 Ω, said resistivity being measured by a device for measuring resistivity on the basis of a four-point measurement with two outer probes, said resistivity being measured on a one-piece top layer of said material with a thickness of at least twice the thickness distance from the outer probes of said device. This thickness requirement is not a requirement of the sputtering target itself. On the other hand, it is a requirement of the measuring method since measuring the resistivity with a four-point measurement on a thinner top layer can lead to inaccurate measurements. Resistance powers in this range are advantageous since such low resistance powers enable the use of DC sputtering, pulsed DC sputtering or AC sputtering at a frequency of less than 350 kHz. Prior art sputtering targets with higher resistivity must generally be used with RF sputtering. RF sputtering has the disadvantage compared to DC or AC sputtering with a frequency lower than 350 kHz that layers can only be formed at a lower speed, that the power unit concerned is more expensive and that forming the layer is more complicated and difficult to control is.
In embodiments, said top layer may have a porosity of less than 10%, preferably less than 7%, more preferably less than 5%, even more preferably less than 3% as measured by a cross-sectional SEM image analysis. This is advantageous because a denser sputtering target has a higher service life / volume ratio and provides better electrical and thermal conductivity. This leads to a more stable sputtering action and the possibility of applying a higher power level at which higher deposition rates are obtained.
In embodiments, said mixture of oxides may account for at least 99 mole%, preferably at least 99.5 mole%; more preferably at least 99.9 mole% of said top layer. It is an advantage of embodiments of the present invention that a top layer with relatively low resistivity comprising a mixture of oxide of Zn, Sn and optionally Ga can be obtained despite a relatively high purity. Baptism (e.g., with Al) to reduce the resistivity of Zn Sn (Ga) -based sputtering targets is therefore not necessary here.
In embodiments, the sputtering target can be of any shape that is considered useful in the art. However, a cylindrical shape is preferred because it is rotatable without creating inhomogeneities in the sputtered layer, and where a high uptime becomes possible thanks to the large material depot and high target use as well as very low particle production, combined with increased process stability compared to flat process stability sputter sources.
In embodiments, the sputtering target may further comprise an inner carrier tube and an adhesive layer that adheres said carrier tube to said top layer.
In embodiments, said adhesive layer may be a metal alloy with a melting temperature of higher than 200 ° C, preferably higher than 300 ° C, and more preferably higher than 400 ° C. In embodiments, said alloy can be a Ni alloy. Such an adhesive layer is advantageous since it reduces the risk of defects with respect to adhesive material during sputtering. It also allows the use of higher power densities without melting the bonding material. Higher power densities make higher sputter speeds possible.
In embodiments, the top layer has a density of more than 4 g / cm 3, preferably higher than 5 g / cm 3. A higher density guarantees a longer operating time of the sputtering target. Such high densities are advantageously achieved by the method of the sixth aspect.
In a second aspect, the present invention relates to a process for forming a coating on a substrate by means of sputtering, wherein use is made of a sputtering target according to any embodiment of the first aspect. In other words, this aspect relates to the use of a sputtering target as described herein for forming a layer on a substrate by sputtering.
In embodiments, said sputtering may be DC sputtering, pulsed DC sputtering or AC sputtering with a frequency of less than 350 kHz. This is made possible with the view of the low resistivity of the sputtering targets of the first aspect.
In embodiments, said sputtering can be performed with a power density of at least 6 kW, preferably at least 10 kW, more preferably at least 14 kW and most preferably with at least 18 kW average DC power per meter target length. This is a clear advantage of the present invention that such a high power density can be used. For AC sputtering, the AC power density can be selected as being equivalent to the above-mentioned DC values. The latter can be determined, for example, taking into account the fact that twice the (integrated) power level applied to a dual configuration must correspond to the average DC power density per single target.
In embodiments, the frequency of breakdowns may be lower than 100 pawls / s @ 18kW / m, preferably lower than 60 pawls / s @ 18 kW / m, even more preferably lower than 30 pawls / s @ 18 kW / m, with even more preferably, lower than 10 p-turns / s @ 18 kW / m and most preferably lower than 6 p-turns / s @ 18 kW / m. This is typically higher than 2 passages / s @ 18 kW / m, more typically higher than 3 and even more typically higher than 4 passages / s @ 18 kW / m. For example, it can be between 3 and 7 p-turns / s @ 18 kW / m or between 4 and 6 p-turns / s @ 18 kW / m. punctures are monopolar punctures, i.e. punctures that arise entirely on the top layer of the target material and not between the target material and another mass of the coating system.
In a third aspect, the present invention relates to a substrate with a length of at least 10 cm, preferably at least 20 cm, more preferably at least 30 cm and even more preferably at least 50 cm and an amorphous semiconductor coating on a surface thereof comprising oxides of Zn, Sn and optionally Ga. This amorphous semiconductor coating can be prepared with a target as described in the first aspect.
In embodiments, this coating can be uniform. For example, no visible defects or non-uniformities can be observed with the naked eye.
In embodiments, said coating may have a thickness uniformity characterized by a relative standard deviation of less than 5%, preferably less than 2.5%, more preferably even less than 1.5%. In embodiments, said thickness uniformity can be measured at a distance from the substrate edges, e.g., by excluding 1 cm around the perimeter of the substrate.
It is an advantage of embodiments of the third aspect that a long substrate with a uniform coating can be obtained. In the prior art, since long one-piece oxide targets from Zn, Sn and optionally Ga oxide were particularly problematic to obtain, it was an obvious solution to place shorter top layers side by side on a sputtering target . However, this results in deviating properties as a side effect (for example, but not limited to, thickness uniformity, roughness and defect density) in the coating on the substrate, especially in the area of the substrate corresponding to the area of the connection between the top layers of the sputtering target. By using the long one-piece sputtering targets according to the first aspect of the present invention, proportionally longer substrates can be uniformly coated than was previously the case. However, due to non-uniformity of plasma near the edges of the sputtering target, the length of the substrate that can be uniformly coated according to embodiments of the present invention is typically smaller than the length of the sputtering target and in any case at least 20% of the length of the sputtering target and 10 to 70 cm less than, and more typically 20 to 40 cm less than, the length of the sputtering target. Consequently, a sputtering target according to the first aspect with a size of 50, 60, 70 or 80 cm can produce a substrate according to the third aspect which typically measures 10, 20, 30 or 40 cm respectively. In any case, a sputtering target according to the first aspect of at least 50 cm can produce a substrate according to the third aspect which is at least 10 cm long and in most cases typically 20 cm long.
The substrate can be any substrate. It may, for example, be an insulator such as glass or plastic, a semiconductor such as a silicone wafer or a metal such as steel, which may in each case be flexible or rigid.
In embodiments, in the amorphous semiconductor coating, the amount of Ga in said mixture of oxides relative to the total amount of Ga, Zn and Sn may be between 0 and 20 at% or between 1 and 20 at%, preferably between 3 and 15at %, more preferably between 4 and 9 at%. The presence of Ga in the mixture of oxides of the amorphous semiconductor coating is advantageous because it improves electrical performance. The amount of Zn in said mixture of oxides relative to the total amount of Ga, Zn and Sn can be between 15 and 85 at%, preferably between 30 and 77 at%.
In an embodiment of the third aspect, the relative amount of Sn is between 15 and 55 at%.
In an embodiment of the third aspect, the amount of Zn in said mixture of oxides relative to the total amount of Ga, Zn and Sn can be between 15 and 85 at%, preferably between 45 and 77 at%, more preferably between 56 and 70 at% and the relative amount of Sn may be between 15 and 55 at%, preferably between 28 and 35 at%. This composition was also correlated with good transistor performance.
In embodiments of the third aspect, the mixture of oxides contains zinc stannate oxide.
In an embodiment of the third aspect, the sum of all zinc stannate oxides in mol% present in said amorphous semiconductor coating may be higher than any other oxide present therein. In embodiments, said zinc stannate oxides are typically (> 50 mole%) Zn 2 SnO 4. In embodiments, said zinc stannate oxides are essentially (> 90 mole% and preferably> 95 mole%) Zn 2 SnO 4. In embodiments, said zinc stannate oxides are zinc stannate oxide Zn 2 SnO 4. The fact that the sum of all zinc stannate oxides in mol% present in said amorphous semiconductor coating is higher than any other oxides present therein is advantageous because the inventors could correlate the presence of zinc stannate oxides in the top layer with high top layer quality .
In a fourth aspect, the present invention relates to a thin film transistor comprising a substrate according to any embodiment of the third aspect.
In a fifth aspect, the present invention relates to an active matrix display comprising a thin film transistor according to any embodiment of the fourth aspect.
In a sixth aspect, the present invention relates to a method for producing a sputtering target, said method comprising the steps of: a. Providing a mixture of oxides of zinc, tin and optionally gallium, b. heating said mixture to a temperature above 1000 ° C, preferably to a temperature between 1700 ° C and 2100 ° C or 1800 ° C to 2100 ° C, c. providing a sputtering target substrate, and d. projecting, preferably spraying, said heated mixture onto said sputtering target substrate, said heated mixture cooling and solidifying on said sputtering target substrate.
The method according to the sixth aspect is unique because it makes long sputtering targets possible. The available length of the sputtering targets is at least 30 cm and in some embodiments at least 50 cm as described in the first aspect.
An aspect of the present invention is therefore a sputtering target that is available by embodiments of the method of the sixth aspect.
As far as known to the inventors, other methods known in the art such as sintering do not allow to obtain sputtering targets according to the first aspect. In particular, the top layer will not have the mechanical integrity that permits a one-piece length of at least 50 cm. Even more advantageously, the sputtering target obtained in the sixth aspect of the present invention can be obtained with a low porosity.
In one embodiment, the total duration of the sum of steps b and d can be less than 1 second.
In one embodiment, the method is a thermal spray method. That the targets can be produced by a thermal spray method is surprising in light of the low sublimation or decomposition temperature of Zn and Sn oxides. For example, SnO 2 decomposes at a temperature of about 1080 ° C before melting at 1630 ° C and ZnO sublimates at around 1800 ° C before melting at 1975 ° C. This low sublimation and decomposition temperature has hitherto ruled out thermal spraying as an effective method for forming pure Zn or Sn oxide masses, since thermal spraying generally requires the material to be deposited to be heated at least to its melting point.
In one embodiment, the mixture is supplied in such a way to achieve intimate contact of Sn and Zn oxide components during the melting phase of thermal spraying. Thermal spraying is generally carried out with particles that are sufficiently large and move freely and that are supplied by a supply system. To achieve close contact during melting, the mixture is preferably prepared in such a way that oxides of Zn and SN and optionally Ga are present in single composite particles. In this embodiment, the mixture will include particles that include Zn, Sn, and optionally Ga within the same particle. The way in which the various oxides come into contact with each other within a composite particle is not crucial. For example, one oxide can form one part of a particle and another oxide can form another part of the same particle. This is shown schematically in Figure 12. For example, an oxide may be present as a coating around particles of another oxide. In another example, a particle comprises two separate parts of a different oxide nature bonded together. In yet another example, a particle comprises one oxide that forms a matrix within which islets of another oxide are dispersed.
In embodiments, the amount of composite particles in said mixture of oxides that will be subjected to step b of the sixth aspect may be 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 70% or more or 90% or more of the particles that form said mixture.
Preparing the mixture may, for example, include agglomeration. Agglomeration can be carried out, for example, by compacting into tablets a mixture of particles of an oxide of Zn, particles of an oxide of Sn and optionally particles of an oxide of Ga with sufficient force (e.g. 80 kN), sintering these tablets and then crushing the tablets or, for example, by spray drying. The agglomeration can be carried out from a dry mixture or a wet mixture such as a slurry.
The particles can be dispersed in water with the addition of a chemical binder in such a way that an intimately mixed slurry is obtained that is suitable for such agglomeration.
Preparing the mixture may include, for example, a sintering step in which a mixture (e.g., the above-mentioned agglomerated mixture) comprising oxides of Zn, oxides of Sn and optionally oxides of Ga is sintered. Sintering can, for example, be carried out at a temperature of 600 to 1300 ° C.
In embodiments, it is advantageous that at least one of the oxide particles involved in the preparation of the mixture has a diameter of less than 10 µm, preferably less than 5 µm.
An optional screening step can also be performed to obtain particles with a size distribution suitable for thermal spraying.
A mixture of components in intimate contact in a particle is advantageous since this makes it possible to obtain top layers with a better homogeneity and a better density.
In one embodiment, the mixture is intimate enough to allow the formation of zinc stannate oxide in the top layer. Preferably, the mixture is intimate enough to permit the acquisition of essentially Zn 2 SnO 4 spinel in the top layer. This does not necessarily require the presence of Zn 2 SnO 4 in the particles themselves.
In embodiments, the support tube may be roughened (e.g., by sandblasting) from the sputter target substrate to enhance the interface between the support tube and adhesive layer. This has the advantage of improved thermal and electrical conductivity.
Specific and preferred aspects of the invention are described in the appended independent and dependent claims. Features of the dependent claims can be combined with features of the independent claims and with features of other dependent claims if appropriate and not only if explicitly stated in the claims.
Although improvements, changes and evolutions are perpetually evident in establishments in this area, it is believed that the present concepts essentially represent new and groundbreaking improvements, including deviations from prior art practices, resulting in more efficient, stable and reliable devices of this nature.
The above and other features, characteristics and advantages of the present invention will become apparent in the detailed description below in combination with the accompanying drawings which illustrate, by way of example, the principles of the invention. This description is only given as an example, without limiting the scope of the invention. The reference numbers given below refer to the attached figures.
Brief description of the drawings
FIG. 1 (left) is a schematic representation of a cross-section of a sputtering target tube; FIG. 1 (right) shows an enlarged part of the tube.
FIG. 2 is a cross-sectional micrograph of a top layer of a sputtering target according to an embodiment of the present invention.
FIG. 3 is a cross-sectional micrograph of a top layer of a sputtering target according to an embodiment of the present invention.
FIG. 4 is an XRD spectrum of a top layer of a sputtering target according to an embodiment of the present invention.
FIG. 5 is a cross-sectional micrograph of a top layer according to an embodiment of the present invention.
FIG. 6 is an XRD spectrum of a powder used to form a top layer according to an embodiment of the present invention.
FIG. 7 is an XRD spectrum of a top layer obtained by thermal spraying of the powder of FIG. 6.
FIG. 8 is a cross-sectional micrograph of a top layer obtained by thermal spraying of the powder of FIG. 6 according to an embodiment of the present invention.
FIG. 9 (top) is a transmission spectrum of a layer obtained by sputtering a target with the top layer of FIG. 8 according to an embodiment of the present invention. FIG. 9 (below) shows the same spectrum after baking.
FIG. 10 is an XRD spectrum of a top layer obtained by thermal spraying according to an embodiment of the present invention.
FIG. 11 is a cross-sectional micrograph of the top layer of FIG. 10 according to an embodiment of the present invention.
FIG. 12 is a schematic representation of a single particle comprising an oxide of Zn and an oxide of Sn in the same particle according to embodiments of the present invention.
Description of illustrative embodiments
The present invention will be described with reference to specific embodiments and with reference to certain drawings, but the invention is not limited thereto, but is only limited by the claims. The described figures are only schematic and non-limiting. In the figures, the size of some of the elements can be exaggerated and not drawn to scale for illustrative purposes. The dimensions and the relative dimensions do not correspond to the actual embodiments of the invention.
Moreover, the terms first, second, third, etc. are used in the description and in the claims to distinguish between similar elements and not necessarily for describing a sequence, neither in time, nor in space, nor in terms of interest or in any other way. It is to be understood that the terms used are interchangeable under proper conditions and that the embodiments of the invention described herein are capable of operating in sequences other than those described or illustrated herein.
In addition, the terms bottom, top, top, bottom, etc. in the description and claims are used for descriptive purposes and not necessarily to describe relative positions. It is to be understood that the terms used are interchangeable under proper conditions and that the embodiments of the invention described herein are capable of operating in orientations other than those described or illustrated herein.
It should be noted that the term "comprising" as used in the claims should not be interpreted as being limited to the means specified thereafter; it does not exclude other elements or steps. It must therefore be interpreted as a specification of the presence of the listed features, units, steps or components referred to, but it does not exclude the presence or addition of one or more other features, units, steps or components or groups thereof. Therefore, the scope of the expression "a device comprising means A and B" should not be limited to devices consisting only of parts A and B. It means that with regard to the present invention, the only relevant parts of the device A and B to be.
References in this specification to "one embodiment" or "an embodiment" mean that a particular feature, structure, or feature described in connection with the embodiment is included in at least one embodiment of the present invention. Mentions of the phrase "in one embodiment" or "in an embodiment" at different places in this specification do not necessarily all refer to the same embodiment, but it is possible. Furthermore, the specific features, structures or characteristics may be combined in any suitable manner in one or more embodiments, as will be apparent to those skilled in the art from this disclosure.
In a similar manner, it should be noted that in the description of exemplary embodiments of the invention, various features of the invention are sometimes grouped into a single embodiment, figure, or description thereof to streamline disclosure and understanding of one or more of the various inventive aspects to ease. However, this method of disclosure should not be interpreted as an expression of an intention that the claimed invention requires more features than expressly stated in each claim. As shown in the following claims, the inventive aspects lie in less than all the features of a single preceding disclosed embodiment. Therefore, the claims that follow the detailed description are hereby explicitly included in this detailed description, wherein each claim stands on its own as a separate embodiment of the present invention.
In addition, since some embodiments described herein include some, but not other, features included in other embodiments, combinations of features of different embodiments are intended to fall within the scope of the invention and form different embodiments, as will be understood. by someone who is trained in this field. For example, in the following claims, any of the claimed embodiments can be used in any combination.
In addition, some of the embodiments herein are described as a method or combination of elements of a method that can be implemented by a processor of a computer system or by another means to perform the function. In other words, a processor with the necessary instructions for carrying out such a method or element of a method constitutes a means of carrying out the method or element of a method. Moreover, an element described herein of an embodiment of an apparatus is an example of a means to perform the function realized by the element for the purpose of carrying out the invention.
Numerous specific details are set forth in the description given here. However, it is understood that embodiments of the invention can be worked out without these specific details. In other cases, well-known methods, structures and techniques were not shown in detail in order not to obstruct the understanding of this description.
The following terms are offered only to aid in understanding the invention.
As used herein and unless otherwise specified, the term "mixture of oxides of zinc, tin and optionally gallium" refers to a mixture of two or more oxide compounds comprising at least one oxide compound comprising zinc and at least one oxide compound comprising tin (and optionally an oxide compound comprising gallium), said oxide compound comprising zinc and said oxide compound comprising tin (and said oxide compound optionally including gallium) being either as numerous as there are metals (e.g., two or optionally three) or having a lower number of oxide compounds wherein at least one oxide compound has at least two metals (e.g., Zn 2 SnO 4 or ZnGa 2 O 4).
As used herein and unless otherwise specified, the term "zinc stannate oxide" refers to an oxide compound comprising at least zinc and tin in its composition. A typical example is Zn 2 SnO 4 but other compounds such as non-stoichiometric compounds also fall within this definition.
The invention will now be described with reference to a detailed description of various embodiments of the invention. It is clear that other embodiments of the invention can be configured based on the knowledge of persons skilled in the art without leaving the scope of the invention, the invention being limited only by the conditions of the appended claims.
Examples
Examples 1, 2, 4, 6 and 8 below were performed by thermally spraying a mixture on a sputtering target substrate to obtain a sputtering target 4 as schematically represented in Figure 1. The sputtering target substrate was composed of a support tube 1 and an adhesive layer 2 from a Ni alloy with a high melting point. The carrier tube 1 had a relatively high roughness and the adhesive layer 2 had a thickness of a few hundred µm. The thermal spraying process consisted of accelerating and projecting (in this case spraying) drops of at least partially molten oxide material onto the sputtering target substrate, where they become flat after impact and solidify to form a coating. The powder particles of the base material typically have a size of 10 to 90 microns and flow freely, whereby these powders can be consistently supplied to the spraying device while being transported through a gas, usually argon, via the feed lines and injectors to the device. A plasma spray system was used in these examples. The plasma spray system was operated with a mixture of argon, nitrogen and hydrogen gas with a capacity of 40 to 90 kW. The spray system had a feed capacity of 120 g / min.
Example 1: thermal spraying of a simple powder mixture of ZnO and SnO in an atomic ratio Zn: Sn of 65:35.
Commercial spray-agglomerated and sintered pure ZnO and pure SnO2 particles, each with an average particle diameter of 10 to 90 microns, measured by a Malvern particle size analyzer, were mixed for 20 minutes to a Zn: Sn ratio of 65:35 at% in a rotating mixing pot and then thermally sprayed as indicated above. Such particles for both ZnO and SnO 2 are typically prepared from much finer raw material powder, typically smaller than 5 microns and with a metal purity of 99.99 wt%. The small raw material particles are typically dispersed in water with the addition of a chemical binder, agglomerated by spraying, sintered and then sieved to a particle size suitable for thermal spraying. Figure 2 shows the structure of the top layer after the thermal spraying procedure. The deposited SnO 2 particles were for the most part not melted and no Zn 2 SnO 4 spinel was formed, as measured by X-ray diffraction. The phase homogeneity was considered acceptable, but not optimal. The density of the top layer was less than 4.7 g / cm 3, as measured by an Archimedes method, which is acceptable but also not optimal. The coating had a lower strength and integrity than in the following examples, but still a 30 cm target could be made.
Example 2: thermal spraying of a powder with intimately mixed ZnO and SnO in an atomic ratio Zn: Sn of 41:59.
Commercial spray-agglomerated and sintered SnO 2 powders with an average particle size of 10 to 90 microns from Example 1 were manually mixed for 1 hour with much smaller commercial ZnO particles with an average size of less than 1 micron, sintered for 2 hours and sieved up to a particle size in the range of 10 to 100 microns. This procedure ensured that both Zn and Sn oxide components were present as single particles (see Figure 12). The thermal spraying of this mixture resulted in a top layer comprising a Zn: Sn ratio of 41:59 at%. The strength of the resulting top layer was very good with a porosity of 8.3% and a density of at least 5.11 g / cm 3. Zn and Sn elements were better distributed than in Example 1, as measured by elemental EDX mapping. Figure 3 shows the structure obtained for the top layer when the procedure involves intimate contact of the constituent parts in single particles. White micron particles of SnO 2 were uniformly dispersed in a gray matrix of zinc stannate oxide as measured by EDX. The black areas are porosity. XRD indicated the presence of tin oxide and zinc stannate oxide (Zn 2 SnO 4 spinel and other non-stoichiometric species) in the top layer. No ZnO was found in the top layer of this target. The target had a gray color and parallel dark stripes. A few small pores were visible within said stripes and there were small cracks near the ends of the target. The target was 880 mm long.
Conclusion of examples 1 and 2:
The quality of the mixture was found to have a positive influence on the homogeneity, density and strength of the obtained top layer. It was also shown to have a positive influence on the formation of zinc stannate oxides such as Zn 2 SnO 4 spinel.
Example 3: the use of sputtering targets from example 2 to produce layers on a substrate.
The sputtering target of Example 2 was used to produce sputtered layers via a DC sputtering process. To test the stability of the target, sputtering was performed at 18kW / m for more than 20 hours in an oxygen-free atmosphere. The sputtering process was stable. To produce the layer, the sputtering was performed at 18 kW / m for 1 hour and 20 minutes in an oxygen-free atmosphere. The opening time of the coating device between two depositions was kept as short as possible. The frequency of breakthroughs was approximately 10 pDreams / s @ 18 kW / m. This is a low frequency of breakdowns for such a high power. The maximum scaling speed was 4 kW / min / m. The pressure during deposition was 3.0 * 10 -3 mbar. The deposition rate was 6.5 nm per meter and per minute for a power density of 1 kW / m. No damage, cracks or dusting was introduced on the target. The glass substrate was heated to 400 ° C during the deposition. The table below shows the properties of two samples obtained with the above procedure. "D." appears in this table for thickness, as measured by ellipsometry; "4 p." stands for electrical resistance as measured by four-point measurement; μ is the carrier mobility as measured on the basis of the Hall effect with a "van der Pauw" method; "Gr. XRD" is the phase (amorphous or crystalline) as determined by shearing angle of incidence XRD at an angle of incidence of 0.6 °; "n" stands for refractive index; "k" stands for extinction coefficient as measured by ellipsometry (Sentech) from 190 nm to 2500 nm with an angle of incidence of 50 °; "Am" stands for amorphous; and "Kr." stands for crystalline. The coatings obtained with this procedure were crystalline, which is not optimal for use in semiconductor channel layers in thin film transistors.
Example 4: thermal spraying of SnO 2 powder mixed with ZnO powder in a Zn: Sn ratio of 68:32.
SnC> 2 particles containing ZnO components, as prepared in Example 2, were mixed for 20 minutes in a rotary mixing jar with commercial spray-agglomerated and sintered ZnO particles with a particle size of 10 to 90 microns in such a way as to increase the general Zn content of the mixture to a Zn: Sn ratio of 68:32. The thermal spraying of this mixture resulted in a top layer comprising a corresponding Zn: Sn ratio. The density of the obtained top layer was at least 5.11 g / cm 3. The presence of tin oxide, zinc oxide and zinc stannate oxide (Zn 2 SnO 4 spinel and other non-stoichiometric species) in the top layer was observed (see Figure 4). In Figure 4, the XRD peaks, indicated by an ordinary arrow, correspond to SnO2 in its cassiterite phase; the peaks indicated by an arrow with dashed lines correspond to spinel of the Zn2Sn04 type (or similar but non-stoichiometric species) and the arrows with long bars correspond to ZnO in its hexagonal phase for the top layer in Example 4. Figure 5 shows the structure that was obtained for the top layer. The structure is similar to Example 2 in such a way that white SnCh particles of micron size are uniformly dispersed in a gray matrix of zinc stannate, but this matrix is now interspersed with larger molten ZnO particles. The target had a gray color and parallel dark stripes. A few small pores were visible within said stripes, but there were no cracks. The target was 880 cm long.
Example 5: the use of sputtering targets from example 4 to produce layers on a substrate.
The sputtering target of Example 4 was used to produce sputtered layers via a DC sputtering process analogous to Example 3. To test the stability of the target, the sputtering was performed at 18 kW / m for more than 20 hours in an oxygen-free atmosphere. The sputtering process was stable. To produce the layer, the sputtering was performed at 18kW / m for more than 2 hours and 40 minutes in an oxygen-free atmosphere. The opening time of the coating device between two depositions was kept as short as possible. The pressure during deposition was 3.0 * 10 -3 mbar. The frequency of breakdowns was approximately 15 ppasses / s @ 18kW / m. The maximum scaling speed was 4 kW / min / m. The deposition rate was 6.5 nm per meter and per minute for a power density of 1 kW / m. No damage, cracks or dust formation was observed. The glass substrate was heated to 400 ° C during the deposition. The table below shows the properties of two samples obtained with the above procedure. The samples produced by this procedure show high carrier mobility and are XRD amorphous, suitable for amorphous metal oxide thin film transistors.
Example 6: thermal spraying of powder with intimately mixed ZnO and SnO in an atomic ratio Zn: Sn of 68:32
Agglomerated and sintered powder containing ZnO and SnO2 components in intimate contact within single powder particles were thermally sprayed as indicated above. The Zn: Sn ratio was 68:32. The powder had an average particle diameter of 10 to 90 microns. These thermally sprayed powders are prepared from much finer raw material of less than 5 microns with a metal purity of 99.99 wt%. The small raw material particles are dispersed in such a way that an intimate mixture is obtained that is suitable for agglomeration. The resulting agglomerates are typically sintered at a temperature of no higher than 1300 ° C. A fraction of this powder is sieved to a particle size suitable for thermal spraying as above. The use of such a procedure makes it possible to have Zn and Sn oxide components in close contact with each other within single syringe particles. Z ^ SnCVspinel can be produced during this sintering step of powder production. For the powder in this example, Figure 6 shows the presence of zinc stannate oxide (spinel), while still containing substantial amounts of SnO 2 and ZnO. This powder was used to form a top layer for a sputtering target in an analogous manner to Example 2. The thermal spraying of this mixture resulted in a top layer comprising a Zn: Sn ratio of 68:32. The phase homogeneity of the obtained top layer was very good. The density of the obtained top layer was at least 5.37 g / cm 3. The target had a homogeneous appearance, without stripes, pores or cracks. The target was 880 mm long. Figure 7 shows the spectrum of the resulting top layer. It mainly shows the presence of zinc stannate spinel with only small amounts of SnO 2 and ZnO. It is clear in Figure 8 that this top layer is more phase-homogeneous than the top layer of Figure 5.
Example 7: the use of sputtering target from example 6 to produce layers on a substrate.
The sputtering target of Example 6 was used to produce sputtered layers via a DC sputtering process analogous to Example 5. To test the stability of the target, the sputtering was performed at 18 kW / m for more than 20 hours in an oxygen-free atmosphere. The sputtering process was stable. The frequency of breakthroughs was approximately 5 p-punches / s @ 18 kW / m. This is a very low frequency of breakdowns for such a high power. The maximum scaling speed was 4 kW / min / m. The deposition rate was between 7 and 10 nm per meter and per minute for a power density of 1 kW / m. No damage, cracks or dust formation was observed. Sputtered layers were produced with power densities of 6 to 18kW / m with a pressure of 2-10 "3 to 8-10'3mbar with oxygen in argon gas of 0 to 10%. The substrates were not heated externally during deposition. The samples were however, afterwards baked in a vacuum at 180 ° C. The table below shows the properties of two samples obtained with the above procedure: The transmission spectrum of a 180 nm thick layer on glass, as measured with a spectrophotometer, is shown in Figure 9 (before (top, dotted line with long dashes) and after (bottom, dotted line) baking at 180 ° C). The samples had a high optical transmission. The samples were XRD-amorphous. The initial resistivity of the layer on an Si / SiO 2 substrate suitable for the manufacture of TFTs was in the range of 0.0023 to 0.013 μm
Example 8: thermal spraying of a Ga Oa - ZnO - SnO Intimate mixture in a Ga: Son: Sn atomic ratio of 7:60:33.
Agglomerated and sintered powder containing Zn, Sn and Ga oxide components in intimate contact within single powder particles were thermally sprayed as indicated above. The Ga: Zn: Sn ratio was 7:60:33. A typical procedure was used to prepare agglomerated and sintered powder, where Ga 2 O 3 particles of micron sizes were introduced into the intimate agglomeration mixture. Sintering was typically conducted so that the particles would not break or decompose. A fraction of this powder was sieved to a particle size suitable for thermal spraying as above. The inventors found that the long sintering of an intimate mixture of micron-sized ZnO, SnO2 and Ga2O4 particles at temperatures high enough for substantial Zn2 SnnO4 spinel formation breaks a sintered mass or sintered powder. The breaking would make the powder unsuitable for thermal spraying. Surprisingly, the thermal spraying of this powder with no or only a small amount of Zn2 Sn04 spinel resulted in a uniform and strong top layer consisting mainly of Zn2 Sn04 spinel. The coating can be obtained with a length that is much longer than 50 cm and no upper limit for the length could be detected. The gallium species were well dispersed within the coating as evidenced by the mapping of elements in cross-sectional micrographs. The phase homogeneity of the resulting top layer was good with mainly Zn 2 SnO 4 and smaller amounts of ZnC> 2 and SnCV components. Figure 10 shows the XRD spectrum of the obtained top layer. The Ga oxide is dissolved in the zinc stannate oxide spinel and is therefore not visible in the XRD spectrum. Figure 11 is a cross-sectional micrograph of the top layer of the target. The density of the obtained top layer was at least 5.7 g / cm 3. The target had a macroscopically homogeneous appearance, without stripes, pores or cracks. The target was 880 mm long. The porosity was less than 3%. The resistivity of the target was 1.94 * 10'2 Ω.m.
Example 9: the use of sputter target from example 8 to produce layers on a substrate.
The sputtering target of Example 8 was used to produce sputtered layers via a DC sputtering process analogous to Example 7. To test the stability of the target, the sputtering was performed at 18 kW / m for more than 20 hours in an oxygen-free atmosphere. The sputtering process was stable. The frequency of break-throughs was less than 5 p break-throughs / s @ 18kW / m. This is a very low frequency of breakdowns for such a high power. The maximum scaling speed was 4 kW / min / m. The deposition rate was between 7 and 10 nm per meter and per minute for a power density of 1 kW / m. No damage, cracks or dust formation was observed. Sputtered layers were produced with capacities of 6 to 18 kW / m with a pressure of 2 x 0 3 to 8-10 x 3 mbar with oxygen in argon gas of 0 to 10%. The substrates were not heated externally during the deposition. The samples were subsequently baked out in a vacuum at 180 ° C. The table below shows the properties of a sample obtained with the above procedure. The transmission spectrum of a 170 nm thick layer on glass, as measured with a spectrophotometer, is shown in Figure 9 (before (top, dotted line with long lines) and after (bottom, full line) baking at 180 ° C). The samples had a high optical transmission. The samples were XRD amorphous. The initial resistivity of the layer suitable for the manufacture of TFTs was in the range of 0.02 to 0.5 Ω.m.
Although preferred embodiments, specific constructions and configurations as well as materials have been discussed herein for devices according to the present invention, it is understood that various changes and modifications may be made to the shape and details without thereby departing from the scope and spirit of this invention. For example, all the formulas mentioned above are just examples of procedures that can be used. Functions can be added to or removed from the block diagrams and operations can be exchanged in the function blocks. Steps can be added to or removed from methods described in the scope of the present invention.
The work that led to this invention was subsidized by the Seventh Framework Program of the European Community (FP7 / 2007-2013) under Grant Agreement No. NMP3-LA-2010-246334.

权利要求:
Claims (17)
[1]
CONCLUSIONS
A sputtering target with a one-piece top layer comprising a mixture of oxides of zinc, tin and optionally gallium, characterized in that said one-piece top layer has a length of at least 80 cm.
[2]
The sputtering target according to claim 1, wherein the amount of Ga in said mixture of oxides relative to the total amount of Ga, Zn and Sn is between 3 and 15 at%, preferably between 4 and 9 at%.
[3]
The sputtering target according to claim 1 or claim 2, wherein the amount of Zn in said mixture of oxides relative to the total amount of Ga, Zn and Sn is between 15 and 85 at%, preferably between 56 and 70% at% and wherein the relative amount of Sn in said mixture of oxides with respect to the total amount of Ga, Zn and Sn is between 15 and 55 at%, preferably between 28 and 35 at%.
[4]
The sputtering target according to any of the preceding claims, wherein the sum of all zinc stannate oxides in at% present in said top layer is higher than any other oxide present therein.
[5]
The sputtering target according to any of the preceding claims, wherein the material comprising said one-piece top layer has a resistivity of less than 10 µm, preferably less than 1 µm, more preferably less than 0.1 µm, most preferably lower than 3 * 10 O * 2 Qm, said resistivity being measured by a device for measuring resistivity on the basis of a four-point measurement with two outer probes, said resistivity being measured on a one-piece top layer of said material with a thickness of at least twice the distance of the outer probes of said device.
[6]
The sputtering target of any one of the preceding claims, wherein said top layer has a porosity of less than 10%, preferably less than 5%, more preferably less than 3% as measured by a SEM cross-sectional image analysis.
[7]
The sputtering target according to any of the preceding claims, wherein said mixture of oxides accounts for at least 99 at%, preferably at least 99.5 at%, more preferably 99.9 at% of said top layer.
[8]
The sputtering target according to any one of the preceding claims, wherein the sputtering target has a cylindrical shape.
[9]
The sputtering target according to any of the preceding claims, wherein the sputtering target further comprises an inner support tube and an adhesive layer which adheres said support tube to said top layer, said adhesive layer being a metal alloy with a melting temperature of more than 200 ° C, preferably of more than 300 ° C and more preferably of more than 400 ° C.
[10]
A process for forming a coating on a substrate by means of sputtering, wherein use is made of a sputtering target according to one of claims 1 to 9.
[11]
The process of claim 10, wherein said sputtering is DC sputtering, pulsed DC sputtering or AC sputtering at a frequency of less than 350 kHz.
[12]
The process of claim 10, wherein said sputtering is performed at a power density of at least 10 kW average DC power per meter target length.
[13]
A substrate with a length of at least 10 cm, preferably at least 30 cm and more preferably at least 50 cm and an amorphous semiconductor coating on a surface thereof, said coating having a thickness uniformity characterized by a relative standard deviation of less than 5%, preferably less than 2.5% and most preferably less than 1.5%, comprising oxides of Zn, Sn and optionally Ga.
[14]
A thin film transistor comprising a substrate according to claim 13.
[15]
An active matrix display device comprising a thin film transistor according to claim 14.
[16]
A method of producing a sputtering target, said method comprising the steps of: a. Providing a mixture of oxides of zinc, tin and optionally gallium, said mixture comprising particles comprising oxides of Zn, Sn and optionally Go within the same particle, b. heating said mixture to a temperature above 1000 ° C, c. providing a sputtering target substrate, and d. projecting, preferably spraying, said heated mixture onto said sputtering target substrate, said heated mixture cooling and solidifying on said sputtering target substrate.
[17]
A method according to claim 16, wherein the total time required for the sum of steps b and d is less than 1 second.

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