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Controversy Surrounds Blockbuster Superconductivity Claim

2023-03-11
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This week researchers claimed to have discovered a superconducting material that can shuttle electricity with no loss of energy under near-real-world conditions. But drama and controversy behind the scenes have many worried that the breakthrough may not hold up to scientific scrutiny.

“If you were to find a room-temperature, room-pressure superconductor, you’d have a completely new host of technologies that would occur—that we haven’t even begun to dream about,” says Eva Zurek, a computational chemist at the University at Buffalo, who was not involved in the new study. “This could be a real game changer if it turns out to be correct.”

Scientists have been studying superconductors for more than a century. By carrying electricity without shedding energy in the form of heat, these materials could make it possible to create incredibly efficient power lines and electronics that never overheat. Superconductors also repel magnetic fields. This property lets researchers levitate magnets over a superconducting material as a fun experiment—and it could also lead to more efficient high-speed maglev trains. Additionally, these materials could produce super strong magnets for use in wind turbines, portable magnetic resonance imaging machines or even nuclear fusion power plants.

The only superconducting materials previously discovered require extreme conditions to function, which makes them impractical for many real-world applications. The first known superconductors had to be cooled with liquid helium to temperatures only a few degrees above absolute zero. In the 1980s researchers found superconductivity in a category of materials called cuprates, which work at higher temperatures yet still require cooling with liquid nitrogen. Since 2015 scientists have measured room-temperature superconductive behavior in hydrogen-rich materials called hydrides. but they have to be pressed in a sophisticated viselike instrument called a diamond anvil cell until they reach a pressure of about a quarter to half of that found near the center of Earth.

The new material, called nitrogen-doped lutetium hydride, is a blend of hydrogen, the rare-earth metal lutetium and nitrogen. Although this material also relies on a diamond anvil cell, the study found that it begins exhibiting superconductive behavior at a pressure of about 10,000 atmospheres—roughly 100 times lower than the pressures that other hydrides require. The new material is “much closer to ambient pressure than previous materials,” says David Ceperley, a condensed matter physicist at University of Illinois at Urbana-Champaign, who was not involved in the new study. He also notes that the material remains stable when stored at a room pressure of one atmosphere. “Previous stuff was only stable at a million atmospheres, so you couldn’t really take it out of the diamond anvil” cell, he says. “The fact that it’s stable at one atmosphere of pressure, that also means that it’d be easier to manufacture.”

Hydrogen is key to the new material’s superconducting ability and to that of any hydride. In the 1960s researchers first calculated that the metallic form of this element might be a superconductor. The idea is that superconductivity occurs when electrons pair up and form a new state of matter and that this could happen in the soup of electrons that surrounds a metal’s nuclei—particularly when those nuclei belong to ultralight hydrogen atoms. Unfortunately, making those atoms shift their phase from gas to metal would require extreme pressure—about one and a half times greater than pressures at the center of this planet. But if a hydrogen atom is combined with one or two other elements in the form of a hydride, researchers think the other atoms would compress the hydrogen, allowing it to attain a metallic state at lower, much more easily obtainable pressures. “We wanted to find the right rare-earth material to mimic these same metallic hydrogen properties as much lower pressures. So that’s where the lutetium metal came into the picture,” says study co-author Ranga Dias, a physicist at the University of Rochester. “And then the use of nitrogen is to stabilize these structures.”

The material, described in a Nature paper published this week, could raise hopes for other hydrides that lower the pressure requirements still further. Unfortunately, the work is dogged by controversy over previous papers by Dias and study co-author Ashkan Salamat, a physicist at the University of Nevada, Las Vegas. “There are two approaches possible. One is just ignore the past and look at this paper and just see what it is,” says Dirk van der Marel, a professor emeritus at the University of Geneva, who was not involved in the new study. “And if I do that, then it is a great paper.” The authors, he notes, used multiple tests of superconductivity, which provided an “extraordinary richness of data.” But van der Marel does not automatically trust these data, in part because of his experience analyzing previous work from the same authors.

In 2020 Dias, Salamat and their colleagues published a Nature paper describing room-temperature superconductivity in a different material, called carbonaceous sulfur hydride. Jorge Hirsch, a physicist at University of California, San Diego, questioned the appearance of data demonstrating the extent to which the material could become magnetized, referred to as its “magnetic susceptibility,” and called on the authors to release their raw data. This measurement is important because it indicates one sign of a superconductor: the ability to expel a magnetic field, a phenomenon called the Meissner effect. Because this measurement must be made while the superconducting hydride is in a diamond anvil cell, results contain background noise. To remove that noise, researchers take a separate measurement of the background and subtract it from the raw data to give the final magnetic susceptibility value. Dias and Salamat pushed back against Hirsch’s claims and eventually released the requested data. Hirsch and van der Marel worked together to analyze those data and concluded they had been processed in an unconventional way at best or had been manipulated at worst. Dias and Salamat contend that their processing method had been misunderstood.

The controversy drove Nature to retract the 2020 paper in 2022, a decision to which all its authors objected. Dias and Salamat say they stand by their results, and two investigations by the University of Rochester, where Dias works, found no wrongdoing. The authors also say they have rerun the original experiments at two different Department of Energy labs with outside observers present and that this effort verified the original results. “Time is a great peer-review process,” Salamat says. Dias says the researchers have updated their original paper as a preprint and resubmitted it to Nature. Other labs, however, have not been able to replicate the original results independently. But it can take a long time for a lab to reproduce and then test a specific material. The drawn out conflict has involved the release of multiple preprints, with neither side accepting the other’s arguments. And it eventually became so acrimonious that administrators of the preprint server arXiv.org removed papers from both parties and put Hirsch under a temporary publishing ban, which he objected to. “My papers analyzed the data and pointed out inconsistencies,” he says.

Hirsch previously earned a reputation as an outspoken critic of superconductivity research, but he and van der Marel were not the only researchers to investigate these authors. In addition to looking at magnetic susceptibility, James Hamlin, a physicist at the University of Florida, examined the electrical resistance data from the 2020 Nature paper. When a material reaches a superconducting state, its electrical resistance drops to zero. The measurement of this phenomenon does not require any processing to remove background noise like the magnetic susceptibility data do. Yet Hamlin notes that even the resistance data appeared to have undergone this processing, which was not disclosed in the paper. He finds Dias’s and Salamat’s responses to be insufficient explanations of these discrepancies. “They’ve kind of muddied the waters by publishing these things that have the appearance of a scientific argument,” Hamlin says. “But if you actually examine their response..., it just holds no water. And it does not address the concerns” raised by other researchers.

Hamlin went on to analyze a paper that Dias and Salamat published in Physical Review Letters (PRL) in 2021 in which they and their colleagues measured another hydride called manganese sulfide. Hamlin noted similarities between the electrical resistance data in the 2021 paper and those in Dias’s 2013 Ph.D. thesis, which had involved a completely different superconducting material. He shared these concerns with the journal and the paper’s authors. Salamat has since responded, suggesting that even though the two data sets may appear similar, the resemblance is not indicative of copied data. “We’ve shown that if you just overlay other people’s data qualitatively, a lot of things look the same,” he says. “This is a very unfair approach.”

This did not satisfy at least one of Salamat’s co-authors on the PRL paper: Simon A. J. Kimber, a former researcher, was disturbed to hear about the potential problem with the data and agrees with Hamlin’s conclusions. “I’ve been at this game for a long time, and I couldn’t think of a single reasonable explanation as to why those data sets should overlap like that,” he says. “I replied to everybody, to PRL’s editors, and said, ‘I think this should be retracted. I can’t think of any logical reason why this should be—retract, retract, retract.’” According to Jessica Thomas, executive editor at the journal’s publisher, the American Physical Society, editors are currently investigating these claims. “We take allegations of data fabrication very seriously,” she says. “At the same time, professional reputations are at stake, and we have to gather information thoughtfully and accurately. We also strive to ensure that the exchanges remain professional and respectful.”

Given the past controversies, Dias and Salamat took pains to test the new material thoroughly for their new paper, performing three different categories of experiments that suggest superconductivity had occurred. “The key fields that you wanted to provide, in order to prove superconductivity, is electrical resistance goes to zero, magnetic susceptibility—which is a demonstration of this expelling the magnetic fields—and heat capacity measurements. These are three different directions,” Dias says. “In this paper, our group has done all three measurements, including submeasurements,” such as two different measurements of magnetic susceptibility for both continuous and fluctuating fields.

The new paper also provides a “recipe” for other researchers who want to synthesize the new hydride and test it themselves, but the authors have not shared existing samples of the material. They are co-founding a start-up called Unearthly Materials to commercialize room-temperature superconductors and say they do not wish to reveal their intellectual property. “We have incredibly clear, detailed instructions on how to make these materials, like all of our studies. We just ask that the groups that are in denial ... go through the protocols themselves,” Salamat says. “We’re excited to see other groups replicate and push forward the field of high-temperature superconductivity.” Some researchers, such as Kimber, have stated they would not devote time and resources to replicating the results because they do not trust the new paper. But other superconducting labs may make the attempt.

If they do succeed at replicating these results, they could open up fascinating new lines of research. For instance, the exact structure of the new material is not yet fully understood. Salamat has used imaging methods that reveal where the heavy lutetium atoms are within the compound, but the team isn’t yet certain about the configuration of the lighter hydrogen and nitrogen atoms. The material also contains relatively little hydrogen, even though this is the substance that theoretically gives hydrides their superconducting ability. Multiple researchers, including Zurek and Ceperley, were intrigued by this contradiction. It could point to alternate theories for how superconductivity arises in hydride materials.

The big claims made in this paper, as well as past controversies, have raised the bar for proof, says Michael Norman, group leader of the condensed matter theory group at Argonne National Laboratory in Illinois, who was not involved in the new study. But a reluctance to trust results until they are replicated is not unusual in the field of superconductivity. He points to the 1986 discovery of cuprates, which were found to be superconducting at much higher temperatures than previous materials. After it was published, “over the first six months, people pretty much didn’t pay the paper much attention. But then when the result was reproduced by a Japanese group, that’s sort of when everybody jumped into the field,” Norman says. As for the new study, “I’m pretty sure that people will be cautiously optimistic until they see another group reproduce it.”

参考译文
重磅超导声明争议四起
本周,研究人员声称发现了一种超导材料,可以在接近真实世界的条件下,在不损失能量的情况下穿梭电流。但幕后的戏剧性和争议让许多人担心,这一突破可能经不起科学的审查。布法罗大学的计算化学家伊娃·祖雷克没有参与这项新研究,她说:“如果你找到一种室温、室温压力的超导体,你就会有一系列全新的技术出现——我们甚至还没有开始梦想过。”“如果这被证明是正确的,这可能会真正改变游戏规则。”一个多世纪以来,科学家们一直在研究超导体。通过携带电力而不以热量的形式释放能量,这些材料可以创造出令人难以置信的高效电线和永不过热的电子设备。超导体也排斥磁场。这一特性让研究人员可以将磁铁悬浮在超导材料上,作为一个有趣的实验,而且这也可能导致更高效的高速磁悬浮列车。此外,这些材料可以产生超强磁铁,用于风力涡轮机、便携式磁共振成像机甚至核聚变发电厂。此前发现的超导材料只有在极端条件下才能发挥作用,这使得它们在许多现实应用中不切实际。已知的第一个超导体必须用液氦冷却到只比绝对零度高几度。在20世纪80年代,研究人员在一种叫做铜酸盐的材料中发现了超导性,这种材料在更高的温度下工作,但仍然需要液氮冷却。自2015年以来,科学家们已经测量了被称为氢化物的富氢材料的室温超导行为。但它们必须在一种复杂的钳子状仪器中被压制,这种仪器被称为钻石砧室,直到它们的压力达到地球中心附近压力的四分之一到一半。这种新材料被称为氮掺杂氢化镥,是氢、稀土金属镥和氮的混合物。尽管这种材料也依赖于钻石砧单元,但研究发现,它在大约10,000个大气压的压力下开始表现出超导行为,大约比其他氢化物所需的压力低100倍。伊利诺伊大学香槟分校(University of Illinois at Urbana-Champaign)的凝聚态物理学家David Ceperley说,这种新材料“比以前的材料更接近环境压力”,他没有参与这项新研究。他还指出,当储存在一个大气压的房间压力下时,这种材料仍保持稳定。他说:“以前的物质只能在100万个大气压下稳定,所以你不能把它从钻石砧中取出来。”“事实上,它在一个大气压下是稳定的,这也意味着它更容易制造。” 氢是这种新材料的超导能力以及任何氢化物的超导能力的关键。在20世纪60年代,研究人员首次计算出这种元素的金属形式可能是超导体。这个想法是,当电子配对并形成一种新的物质状态时,就会发生超导性,这可能发生在金属原子核周围的电子汤中——尤其是当这些原子核属于超轻氢原子时。不幸的是,要使这些原子从气体相转变为金属相,需要极大的压力——大约是地球中心压力的1.5倍。但是,如果一个氢原子以氢化物的形式与一个或两个其他元素结合,研究人员认为,其他原子会压缩氢,使其在更低、更容易获得的压力下达到金属状态。“我们想要找到合适的稀土材料,在更低的压力下模仿这些相同的金属氢特性。这就是镥金属出现的原因,”研究报告的合著者、罗切斯特大学的物理学家兰加·迪亚斯说。“然后使用氮来稳定这些结构。”本周发表在《自然》杂志(Nature)上的一篇论文描述了这种材料,它可能会让人们对进一步降低压力要求的其他氢化物产生希望。不幸的是,这项工作受到了迪亚斯和该研究合著者、拉斯维加斯内华达大学物理学家阿什坎·萨拉马特之前论文的争议。“有两种可能的方法。一种是忽略过去,看看这篇论文,看看它是什么,”日内瓦大学名誉教授德克·范德马雷尔(Dirk van der Marel)说,他没有参与这项新研究。“如果我做到了,那么这就是一篇伟大的论文。”他指出,作者使用了多次超导测试,这提供了“异常丰富的数据”。但范德马雷尔并不会自动相信这些数据,部分原因是他分析了同一作者以前的工作。2020年,迪亚斯、萨拉马特和他们的同事在《自然》杂志上发表了一篇论文,描述了一种称为碳质硫氢化物的不同材料的室温超导性。加州大学圣地亚哥分校(University of California, San Diego)的物理学家豪尔赫·赫希(Jorge Hirsch)对证明这种材料可以磁化到何种程度的数据提出了质疑,并呼吁作者公布他们的原始数据。这项测量很重要,因为它表明了超导体的一个特征:排出磁场的能力,这种现象被称为迈斯纳效应。由于该测量必须在超导氢化物处于金刚石砧室时进行,因此测量结果包含背景噪声。为了去除噪音,研究人员对背景进行了单独的测量,并从原始数据中减去它,得出最终的磁化率值。迪亚斯和萨拉马特反驳了赫希的说法,最终公布了要求的数据。赫希和范德马雷尔一起分析了这些数据,得出的结论是,这些数据最好的情况是被以非常规的方式处理过,最坏的情况是被操纵过。Dias和Salamat认为他们的处理方法被误解了。 这一争议促使《自然》杂志在2022年撤回了2020年的论文,这一决定遭到了所有作者的反对。迪亚斯和萨拉玛特表示,他们坚持自己的结果,迪亚斯工作的罗切斯特大学的两项调查也没有发现任何不当行为。作者还说,他们在能源部的两个不同实验室重新进行了最初的实验,有外部观察员在场,这一努力证实了最初的结果。萨拉马特说:“时间是一个很好的同行评审过程。迪亚斯说,研究人员已经将他们的原始论文更新为预印本,并重新提交给《自然》杂志。然而,其他实验室还不能独立地复制最初的结果。但实验室需要很长时间来复制并测试特定的材料。这场旷日持久的冲突涉及到多份预印本的发布,双方都不接受对方的论点。最终,双方的争吵变得如此激烈,以至于预印本服务器arXiv.org的管理员删除了双方的论文,并对赫希实施了临时发表禁令,赫希对此表示反对。“我的论文分析了数据并指出了不一致之处,”他说。赫希以前以直言不讳地批评超导研究而闻名,但他和范德马雷尔并不是唯一调查这些作者的研究人员。除了研究磁化率,佛罗里达大学的物理学家詹姆斯·哈姆林(James Hamlin)还研究了2020年《自然》杂志论文中的电阻数据。当材料达到超导状态时,其电阻降为零。这种现象的测量不需要像磁化率数据那样去除背景噪声。然而,哈姆林指出,即使是电阻数据似乎也经历了这种处理,这在论文中没有披露。他发现迪亚斯和萨拉马特的回答不足以解释这些差异。哈姆林说:“他们发表这些表面上是科学论证的东西,有点把水搅浑了。”“但如果你仔细观察他们的反应……在美国,它就是装不下水。它并没有解决其他研究人员提出的担忧。Hamlin接着分析了Dias和Salamat于2021年在《物理评论快报》(PRL)上发表的一篇论文,他们和同事在论文中测量了另一种名为硫化锰的氢化物。哈姆林指出,2021年论文中的电阻数据与迪亚斯2013年博士论文中的电阻数据有相似之处,后者涉及一种完全不同的超导材料。他把这些担忧告诉了该杂志和论文作者。Salamat随后回应称,尽管这两组数据可能看起来相似,但这种相似并不意味着数据是复制的。他说:“我们已经证明,如果你只是定性地叠加其他人的数据,很多东西看起来都是一样的。”“这是一个非常不公平的做法。”这至少没有让萨拉马特在PRL论文中的一位合著者满意:前研究员西蒙·a·j·金伯(Simon a . J. Kimber)在听到数据的潜在问题时感到不安,并同意哈姆林的结论。他说:“我在这个领域已经工作了很长时间,我想不出一个合理的解释来解释为什么这些数据集会像这样重叠。”“我回复了所有人,包括PRL的编辑,并说,‘我认为这篇文章应该被撤下。我想不出任何合理的理由来解释为什么要收回,收回,再收回。’”据该杂志出版商美国物理学会的执行主编杰西卡·托马斯(Jessica Thomas)说,编辑们目前正在调查这些说法。她表示:“我们非常严肃地对待有关数据造假的指控。”“与此同时,职业声誉受到威胁,我们必须仔细而准确地收集信息。我们还努力确保交流保持专业和尊重。” 鉴于过去的争议,迪亚斯和萨拉马特煞费苦心地为他们的新论文彻底测试了新材料,进行了三个不同类别的实验,表明已经发生了超导现象。“为了证明超导性,你想要提供的关键场是电阻趋于零,磁化率(这是驱逐磁场的一个演示)和热容测量。这是三个不同的方向,”迪亚斯说。“在这篇论文中,我们的团队已经完成了所有三次测量,包括子测量,”比如连续场和波动场的磁化率的两种不同测量。这篇新论文还为其他想要合成新型氢化物并自行测试的研究人员提供了一个“配方”,但作者没有分享现有的材料样本。他们正在联合创办一家名为unearthearthmaterials的初创公司,将室温超导体商业化,并表示他们不希望透露自己的知识产权。“就像我们所有的研究一样,我们对如何制作这些材料有非常清晰、详细的说明。我们只是要求那些否认事实的团体……他们自己也要遵守协议,”萨拉马特说。“我们很高兴看到其他团队复制并推动了高温超导领域的发展。”一些研究人员,如Kimber,表示他们不会投入时间和资源来重复这些结果,因为他们不信任这篇新论文。但其他超导实验室可能会进行尝试。如果他们真的成功地复制了这些结果,他们可能会开辟令人着迷的新研究方向。例如,新材料的确切结构还没有被完全理解。Salamat使用成像方法揭示了化合物中较重的镥原子的位置,但该团队还不确定较轻的氢原子和氮原子的结构。这种材料也含有相对较少的氢,尽管氢是理论上赋予氢化物超导能力的物质。包括Zurek和Ceperley在内的许多研究人员都对这种矛盾感兴趣。它可以为氢化物材料中超导性的产生提供另一种理论。伊利诺斯州阿贡国家实验室凝聚态理论小组的组长迈克尔·诺曼(Michael Norman)说,这篇论文中提出的重大主张,以及过去的争议,提高了证明的标准,他没有参与这项新研究。但在超导领域,不愿相信结果直到它们被复制是很常见的。他指出,1986年发现了铜酸盐,发现它在比以前的材料高得多的温度下具有超导性。论文发表后,“在最初的六个月里,人们几乎没有太关注这篇论文。但当一个日本小组复制了这一结果时,所有人都投入到了这个领域。”诺曼说。至于这项新研究,“我很确定,在看到另一组人重现它之前,人们会谨慎乐观。”
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