Patent Grant
10892097
This patent application is a national phase filing under section 371 of PCT/EP2017/050794, filed Jan. 16, 2017, which claims the priority of German patent application 10 2016 103 949.7, filed Mar. 4, 2016, each of which is incorporated herein by reference in its entirety.
The invention relates to dielectric ceramic compositions having improved electrical and mechanical properties, for example, for HF components, and to a method for the production of such compositions and to possible uses of such compositions.
Ceramic dielectrics can be used as insulating materials in electrical components, for example, as substrate materials. There is a frequent need for materials with a low dielectric constant and a small dissipation factor or high quality factor Q, for example, for use in waveguides, strip-line filters, dielectric resonators, substrates for integrated circuits etc. The group of materials which exhibits good characteristics in particular in a frequency range between 0.5 GHz and 100 GHz is, however, limited.
It is possible to use polymer materials as dielectrics in such components. In comparison with polymer materials, however, ceramic materials generally have greater long-term stability thanks to lower material degradation (for example, due to UV radiation, heat or cold), are more insensitive to moisture, have elevated gas tightness and therefore enable overall higher component reliability.
However, the dielectric constants of ceramic materials are higher than those of organic, polymer-based materials.
Conventional ceramic materials are, for example, cristobalite (a modification of silicon dioxide), tridymite (another modification of silicon dioxide SiO2), cordierite (a magnesium-aluminum silicate), willemite (a silicate of the stoichiometric composition Zn2[SiO4]), mullite (a silicate comprising aluminum), forsterite (a silicate with the stoichiometric composition Mg2SiO4), aluminum nitride (AlN), corundum (Al2O3) and vitreous ceramics. Only the materials cristobalite, tridymite, cordierite, willemite and vitreous ceramics have a dielectric constant which is less than 7. Cristobalite and tridymite are metastable and exhibit a phase transition in the range between 300° C. and 600° C. Cordierite is a material with a high dissipation factor and a very low thermal coefficient of expansion (TCE) of 0.5 ppm/K. Low thermal coefficients of expansion are problematic because they lead to severe thermomechanical stresses in the event of temperature fluctuations. The low thermal coefficient of expansion of willemite likewise restricts the use thereof.
There is therefore a desire for dielectric materials with a low dielectric constant and small dissipation factor, in particular in frequency ranges beyond 1 GHz. The material may furthermore be RoHS-compliant, i.e., compliant with the Restriction of Hazardous Substances Directive. The thermal coefficient of expansion may furthermore be sufficiently high.
In particular, the dielectric constant should be 7, the quality factor, for example, at 10 GHz, 16,000 and the thermal coefficient of expansion 8 ppm/K.
Moreover, specific density may be as low as possible in order to minimize the weight of components manufactured therefrom. There is furthermore a desire for dielectric ceramic compositions which can be obtained from commonly occurring starting materials.
The composition may also have low sensitivity to contaminants. In other words, contamination with additional substances may modify the essential characteristics of the composition at most to a tolerable extent.
Various embodiments provide a method for producing such dielectrics and various other embodiments provide ceramic components with improved mechanical and electrical characteristics which are based on corresponding dielectrics.
The ceramic composition comprises a main component and a remainder. The composition of the remainder is substantially determined by contaminants during production. The dominant component of the composition is the main component and has the quantity ratio:
Mg(1+x)(1−y)O3+xA(1+x)ySi(1−z)Dz;
x is here a real number which is ≥0.01 and ≤0.3; y is a real number which is ≥0 and ≤0.2; and z is a real number between 0 and 1.
The main component of the ceramic composition thus predominantly comprises Mg (magnesium), O (oxygen), a further element A, Si (silicon) and a further remainder D. Possible and advantageous elements for A and for D are stated further below.
In a simple composition, the ceramic composition is thus obtained as a non-stoichiometric magnesium silicate.
The number x states the relative quantity of MgO which is present as an excess in the ceramic composition. The number y states the relative quantity of the element represented by A which can replace Mg. The number z states the relative quantity of the element represented by the symbol D which can replace Si.
The improved electrical and mechanical properties of the stated ceramic composition are surprising. Investigations into the ceramic compositions forsterite (Mg2SiO4) and enstatite (MgSiO3) (for example, “Effect of Mg/Si Ratio on Microwave Dielectric Characteristics of Forsterite Ceramics”; K. X. Song, X. M. Chen, X. C. Fan; J. Am. Ceram. Soc, 90 [6] 1808-1811 (2007); “Synthesis and Microwave Dielectric Properties of MgSiO3 Ceramics”; M. E. Song, J. S. Kim, M. R. Joung, S. Nahm, Y. S. Kim, J. H. Paik, B. H. Choi; J. Am. Ceram. Soc, 91[8] 2747-2750 (2008)) have revealed the electrical characteristics of these ceramics. Enstatite and forsterite can be associated with different crystal structures on the basis of their differing stoichiometric compositions. The dielectric quality of ceramics with 2 crystal phases can vary monotonically as a function of composition from a relatively low value to a higher value or through a minimum. This minimum can be very flat or also highly pronounced. This is explained by dielectric losses at grain boundaries between two non-identical phases. The more such grain boundaries are present, the greater is the contribution to the overall losses which occur. If such a minimum of dielectric quality is present, it is in a ceramic composition having a maximum of grain boundaries. Both enstatite and forsterite have a relatively high dielectric. A composition which contains less Mg than stoichiometric forsterite would therefore have substantially impaired quality in comparison with a stoichiometric forsterite ceramic. It was therefore to be expected for the electrical quality of a ceramic composition at a 1:1 ratio of Mg and Si (enstatite) and at a 2:1 ratio of Mg and Si (forsterite) to have local maxima. At mixture ratios between 1:1 and 2:1, impairment of the electrical characteristics was therefore to be expected. Electrical quality would decline between these ratios.
It has, however, now been found that, on the basis of the 1:1 ratio of enstatite, increasing the concentration of Mg to ratios between 1:1 and 2:1 unexpectedly improves electrical quality.
It is possible for the value of x to be ≥0.02 and ≤0.08. Over this range of values of x, the ceramic composition has a particularly small dielectric constant and simultaneously a high electrical quality factor Q, for example, Q*f=160 THz to 200 THz (and potentially even up to 220 THz). By way of comparison, literature values for enstatite are about Q*f=120 THz.
Quality values Q*f of 160 THz are here even possible at a relatively high level of contaminants, which demonstrates how well the electrical quality withstands contaminants.
It is possible for x to amount to 0.17. In this case, the ceramic composition can have a density of 3.039 g/cm3. The dielectric constant can amount to 6.63.
It is furthermore possible for x to have the value 0.04. In this case, a specific density of 3.06 g/cm3 on the one hand and a dielectric constant of 6.57 on the other hand can be obtained. When x=0, the specific density can amount to 3.06 at a dielectric constant of 6.2, wherein the quality factor is reduced in comparison with higher values of x.
It is possible for A, in conjunction with an oxygen atom, to form a divalent oxide AO. A can here be selected from Zn (zinc), Ni (nickel), Co (cobalt), Mn (manganese) and a mixture of Zn, Ni, Co, Mn. The corresponding divalent oxide would then in each case be ZnO (zinc oxide), NiO (nickel oxide), CoO (cobalt oxide) or MnO.
It is possible for D together with O2 to represent a tetravalent oxide. D can here in particular be selected from Ti (titanium), Sn (tin), Zr (zirconium) and a mixture of Ti, Sn and Zr. The corresponding tetravalent oxide would then in each case be TiO2, SnO2 or ZrO2.
It is possible for the remainder to contain production-related contaminants. Starting materials for producing the above-stated ceramic composition can be ground to powder with mills, for example, ball mills, tumbling mills, tube mills, attritor mills etc. Abrasion products, for example, from zirconium oxide balls, here virtually inevitably get into the starting products of the ceramic composition and contaminate the composition.
Insensitivity of the electrical and mechanical properties of the ceramic composition to such contaminants may be important. In this manner, qualities of around Q*f=160 THz are readily achievable despite contaminants.
The remainder of the composition can contain corresponding proportions of Al2O3, ZrO2, TiO2, Nb2O5 or Ta2O5.
The remainder can contain divalent elements. The remainder can furthermore contain divalent elements such as Ca (calcium), Sr (strontium) and/or Ba (barium). Calcium, strontium or barium can in each case be present in a proportion of 0.3 mol % or less based on the total composition.
It is possible for the ceramic composition to consist to an extent of 95 mol % or more of the main component.
One possible ceramic composition has a dielectric constant of ≤7 in the frequency range between 0.5 GHz and 100 GHz. The quality factor Q has a value of 16000 or above at 10 GHz. The thermal coefficient of expansion is 8 ppm/K. The specific density is 3.5 g/cm3.
A method for the production of a ceramic composition comprises the steps of: providing calcined powders comprising MgO, AO, SiO2, DO2, combining the powders with a bonding agent and producing pressable pellets, pressing the pellets, decarbonizing the pressed pellets, sintering, wherein A is selected from Zn, Ni, Co and a mixture of Zn, Ni, Co, D is selected from Ti, Sn, Zr and a mixture of Ti, Sn, Zr.
It is here possible for the calcined powders to be provided in the frequency ratio
(1+x)[(MgO)1−y+(AO)y]+(SiO2)(1−z)+(DO2)z;
with 0.01≤x≤0.30; 0.00≤y≤0.20; and 0.00≤z≤1.00.
As an alternative to pressing the pellets, an extrusion method can also be used.
The composition can also be produced by means of film casting. This type of production is preferable if multilayer substrates are to be produced.
A ceramic composition as stated above can be used as a dielectric, for example, in a waveguide, a strip-line filter, a microwave ceramic filter, a dielectric resonator, a substrate for integrated circuits or a multilayer substrate for integrated circuits with integrated passive circuit elements.
The corresponding electrical components can be provided for use in a frequency range between 0.5 GHz and 100 GHz.
An illustration of the stoichiometric ratios of the ceramic compositions as well as schematic components to clarify the application by way of example are shown in the figures to facilitate understanding of the principle on which the composition is based.
In the figures:
The ceramic composition and the use of the ceramic composition and the method for the production of a ceramic composition are not limited to the described embodiments and the exemplary embodiments shown. In particular, thanks to the stability of the electrical and mechanical properties of the composition, both the main component and the remainder of the composition can comprise further elements. Use in further HF components is likewise possible.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2016 103 949 | Mar 2016 | DE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/050794 | 1/16/2017 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2017/148606 | 9/8/2017 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 7138352 | Lee | Nov 2006 | B2 |
| 7378363 | Zheng | May 2008 | B2 |
| 20020002108 | Kim et al. | Jan 2002 | A1 |
| 20030116891 | Okuyama | Jun 2003 | A1 |
| 20110236634 | Kawano | Sep 2011 | A1 |
| Number | Date | Country |
|---|---|---|
| 0304647 | Mar 1989 | EP |
| 2371787 | Oct 2011 | EP |
| H09175856 | Jul 1997 | JP |
| H09175858 | Jul 1997 | JP |
| 2001060914 | Mar 2001 | JP |
| 2001278663 | Oct 2001 | JP |
| 2003004594 | Jan 2003 | JP |
| 2004168579 | Jun 2004 | JP |
| 2008069056 | Mar 2008 | JP |
| 2010024082 | Feb 2010 | JP |
| 2010024083 | Feb 2010 | JP |
| 2010061842 | Apr 2012 | WO |
| 2017148607 | Sep 2017 | WO |
| Entry |
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| Number | Date | Country | |
|---|---|---|---|
| 20190013149 A1 | Jan 2019 | US |
