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PhyandEE
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Re: ReRAM
PhyandEE   10/9/2013 10:54:09 PM
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Nonvolatile said my HRTEM comment on the filament observation is rather speculative, Resistion said Nonvolatile is priori in his NiO devices, and Ron Neal said it is like a Conundrum.

It is interesting. I have collected a bunch of papers on this topic. In the reports, filament size ranges from microns to nano, and to atomic scale. HRTEM and CAFM are the two facilities frequently used. There are also some theoretical modeling works.

No matter what, as Nonvolatile has said, DATA talks, I think we should see the data first. The outstanding device performance as described is a good news to the resistive switching study. I have to mention that although it is difficult to observe the filaments through HRTEM, it does not mean that filament should or should not work. For this reason, I think the work by nonvolatile has good chance to be accepted. It is not the kind of works by HP.

nonvolatile
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Re: ReRAM
nonvolatile   10/9/2013 11:58:01 PM
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It is not possible to look at this matter with the eyes of an indepemdemt electron description. That is, without the ability to show that the change in oxidation number is the result of electron localization, which causes the repulsive coulombic force responsible for the charge gap, one can go around circles. The disproportionation reaction is responsible for the charge gap. It is completely not dependent on position of the Ni ion, so that, after the defects such as oxygen vacancies are compensated by trapped electrons, it is totally possible to have a local MIT which would complete the filament or break it. This can be easily be missed measured as a redox reaction, if you are just checking the oxidation number -like EELS. So, it is not an easy thing to be 100% sure. Other approaches in the electrical measuremnt must be taken. One example is to measure the capacitance of the insulating state as a function of frequency. You can immediately see that the low frequency CV plot is hysterectic due to interfacial polarization and this causes the Vset and Vreset  divergence. This also show that the many oxydation states on the surface of a non compensated NiO is to blame. On the other hand, the compensated NiO is a smooth CV plot without hysteresis. 

I am not at liberty tight now to disclose a few other things. This will come out in due time. But, as we all know, the conductivity is always proportional to DOS. If you use the independent electron approximation (typical of metals and semiconductor), you can never show the f=non-rigid DOS afforded by TMOs. Only if you let DOS=0 and DOS= finite, that you can show the teo states - insulating and metal. Thus, it does not matter if you have filaments or not to have these two states. Somewhere in the filament model, where the filament is broken, an oxidation number-disproportionation -reaction will contribute to the closing and opening of the filament. Thus, as Ron says, this is a conundrum, until you get to reliability. Then, when you see your off state unstable with temperature and your Vset/Vreset variations, you would ask, How cab I control this? well, with the right device physics. Which then requires the stable material to satrt with. Off coarse we do not erradicated all defects, but enough to have a better device and one that we do not have to breakdown the oxide and have these filaments inside the material as the only means of switching. Thus, let us say that we have "quantum scale" filaments....still, how do the close and open? with a in-loco disproportionation. So, why not make the bulk all like that to start with. 

Honestly, we can dope the device to the tipping point that we have a soft electroforming like behavior - sort of born-off. One could interpret that such a device has Nanofilaments. Thus, after a slightly higher voltage than the norma set voltage, the device works just fine. But, if you go a litlle more in doping, it is no longer the case and you have a born-on device. So, the ability to go from always conductive down to just insulating enough to need a little push, is for me a clear demonstration that we have a point. Doping can eliminate the need for filaments. Thus, I am  not so worried about this. It may even be possible that the filaments are doped grain boundaries. Still, doping with CO passivates the device and yields control.

resistion
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nickel vacancies
resistion   10/10/2013 3:36:06 AM
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I just recalled some papers mentioning nickel vacancies in NiO, maybe CO doping eliminates O vacancies but adds Ni vacancies?

nonvolatile
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CEO
Re: nickel vacancies
nonvolatile   10/15/2013 7:47:15 AM
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Thank you for your question. We can see that when the CO level, introduced in the oxide by wet chemistry (i.e., already in solution in the Ni precursor, for Ni(CO)4 is extremely poisonous and not added to the precursor as such-please, anyone trying this DO NOT use Ni(CO)4, it kills), the resulting material is always in a metal-like state. This is very much thickness dependent. Thus, it is not clear if vcancies has anything to do with the metal phase, as a vacancy would be completely screened by the surrounding electrons in the Drude regime. Now, in the less conductive case, it is then possible to have a reversible Mott transition due to the disproportionation reaction of Ni(+2) to Ni(+1) + Ni(+3). The CO doping technology is able to make the disproportionation reaction to be the dominant reaction, which is specifically the charge species that can be reversed without the need of filaments. Because disproportionation reactions are simultaneous oxidation/reduction type of reactions, it can be easily confused with a redox reaction. Redox reactions can occur in severely damaged materials, but they are not very reproduceable. Well then, the CO can be electron donor via a pi bond, and an acceptor in the sigma bond. The other two defect reactions in NiO are Ni(+2) + Vox(+2) --> Ni(+4) + Vox(0){two trapped electrons} and Ni(+2) + 2 e(-) -->Ni(0). The first reaction with oxygen vacancies creates a peak of Ni(+4) in the XRD spectrum. And the metal Ni(0) also shows up in XRD. Both peaks disappear with CO doping, but they are dominant in non-doped materials. Thus, it seems that the pi bond is dominant. It is a possible that in the filamentary versions of NiO, All species occur and we have a situation that the insulating phase dominates at the small areas (the area dependence is very strong, for other reasons). Thus, when the soft breakdown occurs, the filament is strongly Ni(0) and surrounding it, there are many Vox's. Where the filament is disconected - this is seen mostly around the anode - we believe that the "CeRAM effect" (i.e. - a disproportionation/Mott transition) may be occuring to bridge the metal-like filament to the electrodes and create the metal like state of the ReRAM. Extending this to other transition metal oxides, has been achieved by our group.

Thus, I hope that this gives you the general idea. The problem of all ReRAM is the Roff state being unstable with temperature and dispersed in the cummulative probability of good bits. Thus, so far, the dispersion of the off states, specially after many write pulses makes the "freak bits" population too high for commercialization. The other two areas are the high on current and the Vset/Vreset dispersion -specially the Vset dispersion. All these things are extremelly reduced in the CeRAM approach.

As we make a 3 layer structure with Heavy doping/10 nm of low doping/heavy doping, we completely screen the active middle region from the electrodes and be electrode agnostic (CoSi, SiNi, Al..), we have cleaned up the material to have only the right species, lowered Schottky effect, and we are "born on", that is, it is already ohmic as built. The details of this will be coming as we make our next press release - probably late November. (When I said 2 months, it was mid september, so we are delayed a little) - what is holding us back? - everything, including many activities such as ALD and difficulties in nanoscale areas. But, it is going. Thanks for your interest.

 

PhyandEE
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Re: nickel vacancies
PhyandEE   10/16/2013 11:46:49 PM
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What is the resistance switching ratio? Is it uni-polar or bi-polar switching?

nonvolatile
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CEO
Re: nickel vacancies
nonvolatile   10/17/2013 4:38:01 AM
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The ratio is adjustable by doping, but a good number is 10,000 to 1. It is important to have a good Ron that is not to low, as this and Imaxon need to be well controlled. A lower than 100 microamp Imaxon is prefered. Doping for higher Ron, can be easly acomplished by "elemental"doping and does not disturb the the CO doping that heals the coordination sphere of Ni. This is another important aspect - after CO doping, the material is clean, and then one can dope for scateering in the on state independently of anything. It is this bulk control, which cannot be achieved very easily if filaments are just being connected/disconnected in some microscopic area, that makes the coordination control doping so elegant. Thank you for your question.

eavedrop44
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Re: ReRAM
eavedrop44   4/21/2014 4:26:33 AM
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I love what youve got here, love what youre saying and the way you say it. You make it entertaining and you still manage to keep it smart. I cant wait to read more from you. This is really a great blog .
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