SEMICONDUCTOR DEVICE
20170373173 · 2017-12-28
Assignee
Inventors
- Hiromichi OHTA (Sapporo-shi, Hokkaido, JP)
- Takayoshi KATASE (Sapporo-shi, Hokkaido, JP)
- Yuki SUZUKI (Sapporo-shi, Hokkaido, JP)
Cpc classification
H01L29/66
ELECTRICITY
H01L29/24
ELECTRICITY
H10N70/24
ELECTRICITY
International classification
H01L29/66
ELECTRICITY
H01L29/24
ELECTRICITY
Abstract
This semiconductor device comprises an active layer that is formed of an oxide magnetic material and a porous dielectric body that contains water and is provided on the active layer. By using hydrogen and oxygen which are formed by electrolysis of water, the crystal structure of the active layer is changed between a ferromagnetic metal and an antiferromagnetic insulating body.
Claims
1. A semiconductor device comprising: an active layer comprising an oxide magnetic material; and porous dielectrics which contains water and is provided on the active layer, wherein hydrogen ions and hydroxide ions generated by electrolysis of the water are used to change a crystal structure of the active layer between a ferromagnetic metal and an antiferromagnetic insulator.
2. A semiconductor device comprising: a substrate; an active layer which is provided on the substrate and comprises an oxide magnetic material; a source electrode and a drain electrode disposed on the substrate so as to sandwich the active layer; porous dielectrics which contains water and is provided on the active layer; and a gate electrode provided on the porous dielectrics, wherein a voltage is applied to the gate electrode to electrolyze the water, and hydrogen ions and hydroxide ions generated by the electrolyzing is used to change a crystal structure of the active layer between a ferromagnetic metal and an antiferromagnetic insulator.
3. The semiconductor device according to claim 1, wherein an oxygen content of the active layer changes between a ferromagnetic metal and an antiferromagnetic insulator.
4. The semiconductor device according to claim 1, wherein the ferromagnetic metal comprises SrCoO.sub.3 with a perovskite structure, and the antiferromagnetic insulator comprises SrCoO.sub.2.5 with a brownmillerite structure.
5. The semiconductor device according to claim 1, wherein the active layer comprises an oxide represented by ABO.sub.x, where A is Ca, Sr, or Ba; B is Co, Mn, Cr, Fe, or Ni; and 2.0≦x≦3.5).
6. The semiconductor device according to claim 1, wherein the porous dielectrics includes at least one selected from a group consisting of 12CaO.7Al.sub.2O.sub.3, CaO, Al.sub.2O.sub.3, 12SrO.7Al.sub.2O.sub.3, Y.sub.2O.sub.3, HfO.sub.2, SiO.sub.2, MgO, NaTaO.sub.3, KTaO.sub.3, LaAlO.sub.3, ZrO.sub.2, MgAl.sub.2O.sub.4, Nb.sub.2O.sub.5, Ta.sub.2O.sub.5, Si.sub.3N.sub.4, SrTiO.sub.3, BaTiO.sub.3, CaTiO.sub.3, SrZrO.sub.3, CaZrO.sub.3, BaZrO.sub.3, and zeolite.
7. The semiconductor device according to claim 1, wherein the porous dielectrics comprises porous dielectrics in which a hole rate is 5 to 70 vol % and in which a moisture content is 23 to 100 vol %.
8. The semiconductor device according to claim 2, wherein an oxygen content of the active layer changes between a ferromagnetic metal and an antiferromagnetic insulator.
9. The semiconductor device according to claim 2, wherein the ferromagnetic metal comprises SrCoO.sub.3 with a perovskite structure, and the antiferromagnetic insulator comprises SrCoO.sub.2.5 with a brownmillerite structure.
10. The semiconductor device according to claim 2, wherein the active layer comprises an oxide represented by ABO.sub.x, where A is Ca, Sr, or Ba; B is Co, Mn, Cr, Fe, or Ni; and 2.0≦x≦3.5).
11. The semiconductor device according to claim 2, wherein the porous dielectrics includes at least one selected from a group consisting of 12CaO.7Al.sub.2O.sub.3, CaO, Al.sub.2O.sub.3, 12SrO.7Al.sub.2O.sub.3, Y.sub.2O.sub.3, HfO.sub.2, SiO.sub.2, MgO, NaTaO.sub.3, KTaO.sub.3, LaAlO.sub.3, ZrO.sub.2, MgAl.sub.2O.sub.4, Nb.sub.2O.sub.5, Ta.sub.2O.sub.5, Si.sub.3N.sub.4, SrTiO.sub.3, BaTiO.sub.3, CaTiO.sub.3, SrZrO.sub.3, CaZrO.sub.3, BaZrO.sub.3, and zeolite.
12. The semiconductor device according to claim 2, wherein the porous dielectrics comprises porous dielectrics in which a hole rate is 5 to 70 vol % and in which a moisture content is 23 to 100 vol %.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0011]
[0012]
[0013]
[0014]
[0015]
[0016]
[0017]
[0018]
EMBODIMENTS OF THE INVENTION
[0019]
[0020] On the substrate 1 is provided an active layer 2. For the active layer 2, SrCoO.sub.2.5 is used, for example, which is an antiferromagnetic insulator with a brownmillerite structure. The active layer 2 has a film thickness of 30 nm, for example.
[0021] As the material for the active layer 2, other oxides represented by ABO.sub.x (A: Ca, Sr, Ba; B: Co, Mn, Cr, Fe, Ni; 2.0≦x≦3.5) may be used if the characteristics of the material can be changed between a ferromagnetic metal and an antiferromagnetic insulator due to the change in the crystal structure.
[0022] On the active layer 2 is provided a gate insulating film 3, which is a porous insulator. Although, for example, 12CaO.7Al.sub.2O.sub.3 (C12A7) is used for the gate insulating film 3, there may be alternatively used CaO, Al.sub.2O.sub.3, 12SrO.7Al.sub.2O.sub.3, Y.sub.2O.sub.3, HfO.sub.2, SiO.sub.2, MgO, NaTaO.sub.3, KTaO.sub.3, LaAlO.sub.3, ZrO.sub.2, MgAl.sub.2O.sub.4, Nb.sub.2O.sub.5, Ta.sub.2O.sub.5, Si.sub.3N.sub.4, SrTiO.sub.3, BaTiO.sub.3, CaTiO.sub.3, SrZrO.sub.3, CaZrO.sub.3, BaZrO.sub.3, zeolite, or a material containing two or more of these materials. These materials may be in an amorphous state or a crystal state. Alternatively, a resin material such as plastic may be used if the resin material is porous.
[0023] The gate insulating film 3 made of a porous insulator has a plurality of holes formed in the surface or inside thereof, and has a microstructure, which is so-called nanopore or mesopore. The diameters of the holes are 0.3 to 100 nm and preferably are 5 to 20 nm. Further, the hole factor, which is the ratio of the volume of the holes to the volume of the gate insulating film 3, is 5 to 70 vol %, and preferably is 20 to 50 vol %. The holes are spherical, for example, without being limited to that shape.
[0024] The holes in the gate insulating film 3 contain therein water. The moisture content, which is the ratio of the volume of the water contained in the holes to the volume of the holes, is 23 to 100 vol %, preferably is 50 to 100 vol %, and more preferably is 80 to 100 vol %. Note that the moisture content is an average value of the whole gate insulating film 3, and not all the holes have to satisfy the above moisture content.
[0025] The gate insulating film 3 has a film thickness of 200 nm, for example.
[0026] On the substrate 1, there are provided a source electrode 11 and a drain electrode 12 on both sides of the active layer 2, facing each other with the active layer 2 therebetween. Parts of the source electrode 11 and the drain electrode 12 may be sandwiched by the active layer 2 and the gate insulating film 3 therebetween. Further, on the gate insulating film 3 is provided a gate electrode 13. The source electrode 11, the drain electrode 12, and the gate electrode 13 are made of, for example, titanium, gold, nickel, aluminum, or molybdenum.
[0027] As shown in
[0028] Next, operation of the magnetic transistor 100 according to the embodiment of the present invention will be described with reference to
[0029]
[0030] Next, as shown in
[0031] The hydroxide ions having moved to the active layer 2 side react and become water and oxygen, and the oxygen moves into the active layer 2 as shown by arrows 20 in
[0032] In the magnetic transistor 100 having become on-state, even when the voltage applied to the gate electrode 13 is made 0 V, the active layer 2 is maintained to be SrCoO.sub.3, which is a ferromagnetic metal, and the on-state is maintained.
[0033] Next, when a positive voltage of, for example, +80 V is applied to the gate electrode 13 as shown in
[0034] The protons (arrow 21) having moved to the active layer 2 side reduce (draw oxygen) the SrCoO.sub.3 with a perovskite structure, the oxygen content (oxygen nonstoichiometry) of the SrCoO.sub.3 with a perovskite structure is reduced, and the crystal structure is thus changed into SrCoO.sub.2.5 with a brownmillerite structure. As a result, the active layer 2 becomes an antiferromagnetic insulator having an insulation property, and the magnetic transistor 100 thus becomes off-state.
[0035] As described above, in the magnetic transistor 100 according to the embodiment of the present invention, the moisture contained in the gate insulating film 3 made of a porous material is electrolyzed, and the obtained hydrogen and oxygen are used to change an oxygen nonstoichiometric value of the magnetic material oxide constituting the active layer 2 so as to change the crystal structure between a ferromagnetic metal and an antiferromagnetic insulator, whereby the active layer 2 is switched between insulating property and conductive property, and as a result, the magnetic transistor 100 can be turned on and off at a room temperature.
[0036] Note that in order to manufacture the magnetic transistor 100, it is possible to use, as the active layer 2, SrCoO.sub.3, which is a ferromagnetic metal with a perovskite structure, instead of an antiferromagnetic insulator with a brownmillerite structure. In this case, by applying a positive voltage to the gate electrode 13, SrCo03 is reduced and becomes SrCoO.sub.2.5, and the active layer 2 is thus changed from a perovskite structure to a brownmillerite structure. As a result, the active layer 2 is switched from a conductive ferromagnetic metal to an insulating antiferromagnetic insulator. To the contrary, by applying a negative voltage to the gate electrode 13, the active layer 2 is switched from an insulating antiferromagnetic insulator to a conductive ferromagnetic metal.
[0037] Next, with reference to
[0038] Step 1: As shown in
[0039] Step 2: As shown in
[0040] Step 3: As shown in
[0041] Step 4: As shown in
[0042] After the gate insulating film 3 made of a porous insulator is formed, air is introduced into the chamber to set the chamber to a normal pressure, whereby the moisture contained in the air is taken into the holes. The moisture content of the holes becomes 23 to 100 vol %, for example.
[0043] Step 5: As shown in
[0044] Through the above steps, the magnetic transistor 100 according to the embodiment of the present invention is completed.
[0045] Next, the characteristics of the magnetic transistor 100 shown in the following experimental example were compared with the characteristics of a comparative example which does not have a gate insulating film made of a porous material.
Experimental Example
[0046] The magnetic transistor 100 was made as follows. First, a (001) SrTiO.sub.3 single crystal substrate (made by SHINKOSHA CO., LTD., size 10×10×0.5 mm) was prepared, and the active layer 2 made of SrCoO.sub.2.5 and having a film thickness of 30 nm was deposited on the substrate through a metal mask (made by P-One Co., Ltd.) by a pulsed laser deposition method. The substrate temperature was 720° C., and the oxygen pressure was 10 Pa.
[0047] Next, the source electrode 11 and the drain electrode 12 were formed by an electron beam vapor deposition method. The source electrode 11 and the drain electrode 12 were made of titanium, and had a film thickness of 20 nm.
[0048] Next, by a pulsed laser deposition method, a gate insulator 3 made of a porous 12CaO.7Al.sub.2O.sub.3 thin film having a film thickness of 200 nm was formed on the active layer 2. The substrate was not heated, and the oxygen pressure in the chamber was 5 Pa. The channel length (the distance between the source electrode 11 and the drain electrode 12) L and the channel width (the distance between the source electrode 11 and the drain electrode 12) W of the manufactured transistor were both 4.0 mm.
[0049] Finally, the gate electrode 13 made of titanium was formed on the gate insulator 3. By the above process, the magnetic transistor 100 according to the experimental example was manufactured.
Sheet Resistance
[0050] With respect to the magnetic transistor 100, the sheet resistance of the active layer 2 was measured at a room temperature in the state shown in
X-Ray Diffraction
[0051]
[0052] As shown in
[0053] On the other hand, as shown in graph (b), after the negative gate voltage (−50 V) is applied, the peaks represented by symbol P due to a perovskite structure are observed instead of the peaks represented by symbol BM, and it is therefore understood that the active layer 2 has become SrCoO.sub.3 with a perovskite structure.
[0054] As described above, it is understood that the structure of the active layer 2 is changed between brownmillerite SrCoO.sub.2.5 and perovskite SrCoO.sub.3 by changing the gate voltage.
Magnetization Characteristics
[0055]
[0056] As is understood from
Thermopower
[0057] In order to check if the active layer 2 became metal when gate voltage of −50 V was applied to the gate electrode 13 (the case of
[0058] A result of the measurement shows that the thermopower before the application of the gate voltage (the case of
[0059] As described above, in the magnetic transistor 100 of the experimental example, the crystal structure of the active layer is changed between the brownmillerite SrCoO.sub.2.5 structure and the perovskite structure by controlling gate voltage, and the active layer is thus switched between a ferromagnetic metal and an antiferromagnetic insulator, and the transistor operation is possible at a room temperature.
Changes in the Gate Current and the Sheet Resistance with Respect to the Application Time of the Gate Voltage
[0060]
[0061] With reference to
[0062] On the other hand, with reference to
[0063] As described above, it is understood that, in the magnetic transistor according to the embodiment of the present invention, the magnetic transistor 100 can be reversibly turned on and off with a hold time of approximately 2 to 3 seconds also by setting the gate voltage Vg to relatively low voltages of −3 V and +3 V.
The Electron Density and the Sheet Resistance
[0064]
[0065] For example, in the case of the left graph of
[0066] Similarly, in the case of the right graph of
[0067] As described above, it is confirmed that, in the magnetic transistor 100, the oxidation-reduction reaction occurring in the active layer 2 obeys the Faraday's laws of electrolysis.
Comparative Example
[0068] In the sample used for a comparative example, similarly to the experimental example, a (100) SrTiO.sub.3 single crystal substrate (made by SHINKOSHA CO., LTD., size 10×10×0.5 mm) was prepared, and an SrCoO.sub.2.5 epitaxial thin film (film thickness was 40 nm) was formed on the substrate by a pulsed laser deposition method. Next, the substrate was heated in flowing oxygen gas.
[0069] The SrCoO.sub.2.5 epitaxial thin film of such a sample was subjected to an X-ray diffraction measurement and a magnetic characteristics measurement. The X-ray diffraction measurement and the magnetic characteristics measurement were performed in the same way as in the experimental example.
[0070] As a result of the measurement, it was found that when the heating in flowing oxygen gas is performed at a heating temperature of 300° C. or higher, SrCoO.sub.2.5 of the epitaxial thin film became SrCoO.sub.3, and it is possible to control the oxygen nonstoichiometry x in SrCoO.sub.x by the environmental oxygen pressure. On the other hand, when the heating temperature is lower than 300° C., in particular, a temperature close to a room temperature, SrCoO.sub.2.5 of the epitaxial thin film did not become SrCoO.sub.3, and whereby the oxygen nonstoichiometry cannot be controlled.
[0071] That is, it was found that the oxygen nonstoichiometry of SrCoO.sub.x could be controlled only at a high temperature equal to or higher than 300° C. and that, in the vicinity of a room temperature, the crystal structure of the epitaxial thin film cannot not be changed only by controlling the environmental oxygen pressure. That is, with respect to the sample of the comparative example, the active layer cannot be switched, in the vicinity of a room temperature, between a ferromagnetic metal and an antiferromagnetic insulator, the transistor operation is impossible at a room temperature.
DESCRIPTION OF REFERENCE SYMBOLS
[0072] 1 SUBSTRATE [0073] 2 ACTIVE LAYER [0074] 3 GATE INSULATING FILM [0075] 11 SOURCE ELECTRODE [0076] 12 DRAIN ELECTRODE [0077] 13 GATE ELECTRODE [0078] 20 HYDROXIDE ION (OH.sup.−) [0079] 21 PROTON (H.sup.+) [0080] 100 MAGNETIC TRANSISTOR