POSTMODERN ALCHEMY
Researchers unlock secret of gold's light

A.J. Roan, Metal Tech News | Last updated May 07, 2024

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New research on thin gold films has uncovered novel photoluminescence behaviors, advancing understanding of nanoscale chemical reactions and temperature measurement. This breakthrough enhances the use of metals in energy research and offers new methods to probe surface processes crucial for solar fuel development.

Uses quantum mechanics to discover how light makes thin gold films glow.

In a groundbreaking study, researchers at the Swiss Federal Institute of Technology in Lausanne (EPFL) have revealed the quantum secrets behind how light makes thin gold films glow. This discovery, solving a decades-old puzzle, could transform how we make solar fuels and batteries.

Luminescence, the process where substances emit photons when exposed to light, has long been observed in semiconductor materials like silicon. This phenomenon involves electrons at the nanoscale absorbing light and subsequently re-emitting it.

Such behavior provides researchers with valuable insights into the properties of semiconductors, making them useful tools for probing electronic processes, such as those in solar cells.

In 1969, scientists discovered that all metals luminesce to some degree, but the ensuing years have failed to yield a clear understanding as to exactly how this occurs.

Renewed interest in this light emission, driven by nanoscale temperature mapping and photochemistry applications, has reignited the debate surrounding its origins. But the answer was still unclear – until now.

"We developed very high-quality metal gold films, which put us in a unique position to elucidate this process without the confounding factors of previous experiments," said Giulia Tagliabue, head of the Laboratory of Nanoscience for Energy Technologies (LNET) in the School of Engineering at EPFL.

A recent study published in "Light: Science and Applications," details how Tagliabue and the LNET team focused laser beams at the extremely thin – between 13 and 113 nanometers – gold films, and then analyzed the resulting faint glow.

The data generated from their precise experiments was so detailed – and so unexpected – that they collaborated with theoreticians at the Barcelona Institute of Science and Technology, the University of Southern Denmark, and the Rensselaer Polytechnic Institute (USA) to double-check their work and even apply a little quantum science to the mix.

This comprehensive approach allowed them to settle the debate once and for all surrounding the type of luminescence emanating from the films – photoluminescence – which is defined by the specific way electrons and their oppositely charged counterparts (holes) behave in response to light.

This also allowed them to produce the first complete, fully quantitative model of this phenomenon in gold, which can then be applied to any metal.

Unexpected quantum effects

Tagliabue explained that, using a thin film of monocrystalline gold produced with a novel synthesis technique, the team studied the photoluminescence process as they made the metal thinner and thinner.

"We observed certain quantum mechanical effects emerging in films of up to about 40 nanometers, which was unexpected, because normally for a metal, you don't see such effects until you go well below 10 nanometers," she said.

These observations provided important information about where the glowing process happens in gold, which is crucial for using gold as a thermal probe. Additionally, the study unexpectedly found that the light emitted by the gold can indicate how hot its surface is, a valuable discovery for scientists studying at the nanoscale.

"For many chemical reactions on the surface of metals, there is a big debate about why and under what conditions these reactions occur," said Tagliabue. "Temperature is a key parameter, but measuring temperature at the nanoscale is extremely difficult, because a thermometer can influence your measurement. So, it's a huge advantage to be able to probe a material using the material itself as the probe."

Gold standard in solar fuel

In addition to thermal probes, the researchers believe their findings will allow metals to be used to obtain unprecedentedly detailed insights into chemical reactions, especially those involved in energy research.

Metals like gold and copper – LNET's next research target – can trigger certain key reactions, like the reduction of carbon dioxide back into carbon-based products like solar fuels, which store solar energy in chemical bonds.

"To combat climate change, we are going to need technologies to convert CO2 into other useful chemicals one way or another," said LNET postdoc Alan Bowman, the study's first author. "Using metals is one way to do that, but if we don't have a good understanding of how these reactions happen on their surfaces, then we can't optimize them. Luminescence offers a new way to understand what is happening in these metals."

 21ST CENTURY ALCHEMY

Energy scientists unravel the mystery of gold’s glow

EPFL researchers have developed the first comprehensive model of the quantum-mechanical effects behind photoluminescence in thin gold films; a discovery that could drive the development of solar fuels and batteries.

ECOLE POLYTECHNIQUE FÉDÉRALE DE LAUSANNE

Luminescence, or the emission of photons by a substance exposed to light, has been known to occur in semiconductor materials like silicon for hundreds of years. The nanoscale behavior of electrons as they absorb and then re-emit light can tell researchers a great deal about the properties of semiconductors, which is why they are often used as probes to characterize electronic processes, like those occurring inside solar cells.

In 1969, scientists discovered that all metals luminesce to some degree, but the intervening years failed to yield a clear understanding of how this occurs. Renewed interest in this light emission, driven by nanoscale temperature mapping and photochemistry applications, has reignited the debate surrounding its origins. But the answer was still unclear – until now.

“We developed very high-quality metal gold films, which put us in a unique position to elucidate this process without the confounding factors of previous experiments,” says Giulia Tagliabue, head of the Laboratory of Nanoscience for Energy Technologies (LNET) in the School of Engineering.

In a recent study published in Light: Science and Applications, Tagliabue and the LNET team focused laser beams at the extremely thin – between 13 and 113 nanometers – gold films, and then analyzed the resulting faint glow. The data generated from their precise experiments was so detailed – and so unexpected – that they collaborated with theoreticians at the Barcelona Institute of Science and Technology, the University of Southern Denmark, and the Rensselaer Polytechnic Institute (USA) to rework and apply quantum mechanical modelling methods.

The researchers’ comprehensive approach allowed them to settle the debate surrounding the type of luminescence emanating from the films – photoluminescence – which is defined by the specific way electrons and their oppositely charged counterparts (holes) behave in response to light. It also allowed them to produce the first complete, fully quantitative model of this phenomenon in gold, which can be applied to any metal.

Unexpected quantum effects

Tagliabue explains that, using a thin film of monocrystalline gold produced with a novel synthesis technique, the team studied the photoluminescence process as they made the metal thinner and thinner. “We observed certain quantum mechanical effects emerging in films of up to about 40 nanometers, which was unexpected, because normally for a metal, you don’t see such effects until you go well below 10 nm,” she says.

These observations provided key spatial information about exactly where the photoluminescence process occurred in the gold, which is a prerequisite for the metal’s use as a probe. Another unexpected outcome of the study was the discovery that the gold’s photoluminescent (Stokes) signal could be used to probe the material’s own surface temperature – a boon for scientists working at the nanoscale.

“For many chemical reactions on the surface of metals, there is a big debate about why and under what conditions these reactions occur. Temperature is a key parameter, but measuring temperature at the nanoscale is extremely difficult, because a thermometer can influence your measurement. So, it’s a huge advantage to be able to probe a material using the material itself as the probe,” Tagliabue says.

A gold standard for solar fuel development

The researchers believe their findings will allow metals to be used to obtain unprecedentedly detailed insights into chemical reactions, especially those involved in energy research. Metals like gold and copper – the LNET’s next research target – can trigger certain key reactions, like the reduction of carbon dioxide (CO2) back into carbon-based products like solar fuels, which store solar energy in chemical bonds.

“To combat climate change, we are going to need technologies to convert CO2 into other useful chemicals one way or another,” says LNET postdoc Alan Bowman, the study’s first author.

“Using metals is one way to do that, but if we don’t have a good understanding of how these reactions happen on their surfaces, then we can’t optimize them. Luminescence offers a new  way to understand what is happening in these metals.”

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JOURNAL

Light Science & Applications

DOI

10.1038/s41377-024-01408-2 

METHOD OF RESEARCH

Experimental study

ARTICLE TITLE

Quantum-mechanical effects in photoluminescence from thin crystalline gold films

ARTICLE PUBLICATION DATE

19-Apr-2024

21ST CENTURY ALCHEMY

Gold may be key element for cleaner drinking water

UCF researchers are using gold to develop a novel method to remove toxins from drinking water

UNIVERSITY OF CENTRAL FLORIDA

 

IMAGE: 

UCF RESEARCHERS WOO HYOUNG LEE AND YANG YANG ARE LEADING A PROJECT TO USE GOLD TO DEVELOP A NOVEL METHOD TO RID DRINKING WATER OF HARMFUL ALGAL BLOOMS.

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CREDIT: UNIVERSITY OF CENTRAL FLORIDA

Writer: Marisa Ramiccio ’11

ORLANDO, April 18, 2024 – Gold may be a coveted precious metal, but it could also be the key to cleaner drinking water.

A team of UCF researchers is exploring the use of the metal to develop a novel method to rid drinking water of harmful algal blooms, or HABs, which occur when colonies of algae grow out of control and produce toxic or harmful effects on people, fish, birds and other living creatures.

Their project is supported through the U.S. Environmental Protection Agency’s People, Prosperity and the Planet (P3) program, which recently awarded $1.2 million to 16 collegiate teams across the United States.

UCF received $75,000 for their two-year project that aims to develop a gold-decorated nickel metal-organic framework (MOF) that removes microcystins — toxins produced by harmful algae blooms — from the water. MOFs are porous clusters of metal polymers that are used in many practical applications.

The UCF student team includes environmental engineering doctoral student Samuel Adjei-Nimoh, materials science and engineering doctoral student Nimanyu Joshi, and environmental engineering undergraduate students Jennifer Hughes and Julia Going. The principal investigator of the grant is Associate Professor of Environmental Engineering Woo Hyoung Lee, and the co-principal investigator is Associate Professor of Materials Science and Engineering Yang Yang.

“MOFs have been used as a catalyst for many research areas such as hydrogen storage, carbon capture, electrocatalysis, biological imaging and sensing, semiconductors and drug delivery systems,” Lee says. “In this project, we’re using the gold-decorated nickel MOF as a photocatalyst to remove water pollutants.”

The gold will be coated in an MOF, which will help it react to the sunlight. That reaction, known as photocatalysis, will result in the oxidation of the microcystins, removing them from the water.

Microcystins are the most common cyanotoxins linked to harmful algal blooms in freshwater environments, notably in regions such as Florida with abundant lakes. They’re known to cause liver damage, kidney failure, gastroenteritis and allergic reactions in humans. With the UCF team’s novel solution, water treatment facilities can produce cleaner, safer drinking water.

"Clean drinking water isn't just a necessity, it's a fundamental right, especially for Floridians who rely on our abundant lakes and waterways,” Lee says. “By leveraging the innovative nanotechnology for water treatment,  we're not only removing toxins but also safeguarding the health and well-being of our communities, ensuring a brighter, healthier future for all.”

This is Lee’s second consecutive year receiving the P3 award. In 2023, his team was selected for their work on a biosensor that could detect microcystins early in their formation for faster eradication.

This is the 20th anniversary of the P3 program. Projects funded this year will tackle critical issues such as removing PFAS from water, combating harmful algal blooms, and materials recovery and reuse, says Chris Frey, assistant administrator for the U.S. Environmental Protection Agency's Office of Research and Development, in a release.

“I commend these hardworking and creative students and look forward to seeing the results of their innovative projects that are addressing some of our thorniest sustainability and environmental challenges,” Frey says.

About the Researchers

Lee is an associate professor in the UCF Department of Civil, Environmental and Construction Engineering. He received his bachelor's degree in environmental engineering from Chonnam National University in 1996, his master's degree in environmental engineering from Korea University in 2001 and his doctoral degree in environmental engineering from the University of Cincinnati in 2009. Before joining UCF, he was an Oak Ridge Institute for Science and Education postdoctoral research fellow at the U.S. Environmental Protection Agency's National Risk Management Research Laboratory in Ohio.

Yang holds joint appointments in UCF’s NanoScience Technology Center and the Department of Materials Science and Engineering, which is part of the university’s College of Engineering and Computer Science. He is a member of UCF’s Renewable Energy and Chemical Transformation Cluster. Before joining UCF in 2015, he was a postdoctoral fellow at Rice University and an Alexander von Humboldt Fellow at the University of Erlangen-Nuremberg in Germany. He received his doctoral degree in materials science from Tsinghua University in China.

CONTACT: Robert H. Wells, Office of Research, robert.wells@ucf.edu

 

21ST CENTURY ALCHEMY

How to Extract Gold From E-Waste Using Old Milk

ByTasos Kokkinidis
April 13, 2024

Burning the aerogel that had adsorbed and reduced gold from an e-waste solution produced this 0.5 g gold nugget with a purity of around 91%, corresponding to 21 to 22 carats. 

Credit: Raffaele Mezzenga/ETH Zurich

An aerogel made from old milk can extract highly pure gold nuggets from discarded computer motherboards.

Discarded electronics, known as e-waste, often contain large amounts of gold and other heavy metals. Scientists have come up with methods to recover the valuable metals, but these processes often rely on synthetic chemicals that can damage the environment.

Raffaele Mezzenga at ETH Zurich in Switzerland and his colleagues have developed a way to recover gold from e-waste by using a milk-derived aerogel.

He and his colleagues started with whey protein, a byproduct of the cheesemaking industry, and made a low-density aerogel. Making the spongelike material is cheap, he says. “The value of the gold we recover is 50 times the value we invest to transform the protein into this sponge.”

The researchers placed whey protein into an acidic solution and heated it, which unraveled the proteins from tiny balls into strands. Then they freeze-dried the solution, forming a lightweight puck with high porosity.

“You can place them on the top of a flower. And the advantage of having aerogels is that they have high surface area,” says Mohammad Peydayesh, a chemical engineer who’s also part of the research team at ETH Zurich.

The researchers tested the gel’s ability to adsorb gold from a solution also containing other metals—including copper, lead, and nickel—at the same concentration.
Aerogel from old milk sucked up 93 percent of the gold

The aerogel sucked up 93 percent of the gold while removing less than 10 percent of any of the other metals. To test the protein sponge with real e-waste, the team dissolved computer motherboards in aqua regia, a mix of nitric acid and hydrochloric acid.

Gold ions from the mixture settled on the surface of the aerogel and were reduced, forming metallic gold. Each gram of aerogel snatched 190 mg of gold. Burning the aerogel freed the gold, turning it into a tiny hunk of metal.

“It was really exciting to find this nugget in the ashes,” Peydayesh recalls. The nugget was about 91% gold, which corresponds to about 21 to 22 carats.

The method already presents an improvement over activated carbon, a more typical adsorption method used to recover gold. Each gram of activated carbon only adsorbed about 60 mg of gold from an e-waste mixture, the team found. Because it takes a lot of energy to create activated carbon, recovering the same amount of gold using activated carbon had a higher environmental impact in a life cycle analysis.

The team is already eyeing other food waste proteins, such as keratin and those from the production of tofu, that could potentially help with other needs, such as the recycling of rare earth metals.

“We can simultaneously address the global waste of food and e-waste to produce something really precious,” Peydayesh says.

POSTMODERN ALCHEMY

Utilizing palladium for addressing contact issues of buried oxide thin film transistors

TOKYO INSTITUTE OF TECHNOLOGY

 

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A NOVEL METHOD THAT EMPLOYS PALLADIUM TO INJECT HYDROGEN INTO THE DEEPLY BURIED OXIDE-METAL ELECTRODE CONTACTS OF AMORPHOUS OXIDE SEMICONDUCTORS (AOSS) STORAGE DEVICES, WHICH REDUCES CONTACT RESISTANCE, HAS BEEN DEVELOPED BY SCIENTISTS AT TOKYO TECH. THIS INNOVATIVE METHOD PRESENTS A VALUABLE SOLUTION FOR ADDRESSING THE CONTACT ISSUES OF AOSS, PAVING THE WAY FOR THEIR APPLICATION IN NEXT-GENERATION STORAGE DEVICES AND DISPLAYS.

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CREDIT: ASSISTANT PROFESSOR MASATAKE TSUJI AND HONORARY PROFESSOR HIDEO HOSONO

A novel method that employs palladium to inject hydrogen into the deeply buried oxide-metal electrode contacts of amorphous oxide semiconductors (AOSs) storage devices, which reduces contact resistance, has been developed by scientists at Tokyo Tech. This innovative method presents a valuable solution for addressing the contact issues of AOSs, paving the way for their application in next-generation storage devices and displays.

Thin film transistors (TFTs) based on amorphous oxide semiconductors (AOSs) have garnered considerable attention for applications in next-generation storage devices such as capacitor-less dynamic-random access memory (DRAM) and high-density DRAM technologies. Such storage devices employ complex architectures with TFTs stacked vertically to achieve high storage densities. Despite their potential, AOS TFTs suffer from contact issues between AOSs and electrodes resulting in excessively high contact resistance, thereby degrading charge carrier mobility, and increasing power consumption. Moreover, vertically stacked architectures further exacerbate these issues.

Many methods have been proposed to address these issues, including the deposition of a highly conductive oxide interlayer between the contacts, forming oxygen vacancies on the AOS contact surface and surface treatment with plasma. Hydrogen plays a key role in these methods, as it, when dissociated into atomic hydrogen and injected into the AOS-electrode contact area, generates charge carriers, thereby reducing contact resistance. However, these methods are energy-intensive or require multiple steps and while they effectively address the high-contact resistance of the exposed upper surface of the semiconductors, they are impractical for buried contacts within the complex nanoscale architectures of storage devices.

To address this issue, a team of researchers (Assistant Professor Masatake Tsuji, doctoral student Yuhao Shi, and Honorary Professor Hideo Hosono) from the MDX Research Center for Element Strategy at the International Research Frontiers Initiative at Tokyo Institute of Technology has now developed a novel hydrogen injection method. Their findings were published online in the journal ACS Nano on 22 March 2024.

In this innovative method, an electrode made up of a suitable metal, which can catalyze the dissociation of hydrogen at low temperatures, is used to transport the atomic hydrogen to the AOS-electrode interface, resulting in a highly conductive oxide layer. Choosing suitable electrode material is therefore key for implementing this strategy. Dr. Tsuji explains, “This method requires a metal that has a high hydrogen diffusion rate and hydrogen solubility to shorten post-treatment times and reduce processing temperatures. In this study, we utilized palladium (Pd) as it fulfils the dual role of catalyzing hydrogen dissociation and transport, making it the most suitable material for hydrogen injection in AOS TFTs at low temperatures, even at deep internal contacts.”

To demonstrate the effectiveness of this method, the team fabricated amorphous indium gallium oxide (a-IGZO) TFTs with Pd thin film electrodes as hydrogen transport pathways. The TFTs were heat-treated in a 5% hydrogen atmosphere at a temperature of 150 0C for 10 minutes. This resulted in the transport of atomic hydrogen by Pd to the a-IGZO-Pd interface, triggering a reaction between oxygen and hydrogen, forming a highly conductive interfacial layer.

 

Testing revealed that due to the conductive layer, the contact resistance of the TFTs was reduced by two orders of magnitude. Moreover, the charge carrier mobility increased from 3.2 cm2V–1s–1 to nearly 20 cm2V–1s–1, representing a substantial improvement. “Our method enables hydrogen to rapidly reach the oxide-Pd interface even in the device interior, up to a depth of 100 μm. This makes it highly suitable for addressing the contact issues of AOS-based storage devices” remarks Dr. Tsuji. Additionally, this method preserved the stability of the TFTs, suggesting no side effects due to hydrogen diffusion in the electrodes.

Emphasizing the potential of the study, Dr. Tsuji concludes: “This approach is specifically tailored for complex device architectures, representing a valuable solution for the application of AOS in next-generation memory devices and displays.”  IGZO-TFT is now a de facto standard to drive the pixels of flat panel displays. The present technology will put forward its application to memory.

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JOURNAL

ACS Nano

DOI

10.1021/acsnano.4c02101 

METHOD OF RESEARCH

Experimental study

SUBJECT OF RESEARCH

Not applicable

ARTICLE TITLE

Approach to Low Contact Resistance Formation on Buried Interface in Oxide Thin-Film Transistors: Utilization of Palladium-Mediated Hydrogen Pathway

 

Good as gold - improving infectious disease testing with gold nanoparticles

ADVANCED INSTITUTE FOR MATERIALS RESEARCH (AIMR), TOHOKU UNIVERSITY

 

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GNDP PARTICLES

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CREDIT: HIROSHI YABU

By harnessing the power of composite polymer particles adorned with gold nanoparticles, a group of researchers have delivered a more accurate means of testing for infectious diseases.

Details of their research was published in the journal Langmuir.

The COVID-19 pandemic reinforced the need for fast and reliable infectious disease testing in large numbers. Most testing done today involves antigen-antibody reactions. Fluorescence, absorptions, or color particle probes are attached to antibodies. When the antibodies stick to the virus, these probes visualize the virus's presence. In particular, the use of color nanoparticles is renowned for its excellent visuality, along with its simplicity to implement, with little scientific equipment needed to perform lateral flow tests.

Gold color nanoparticles (AU-NP), with their high chemical stability and unique plasmon absorption, are widely employed as probes in immunoassay tests. They exhibit extreme versatility, with their colors fluctuating according to their size and shape. Additionally, their surface can be modified by using thiol compounds.

Conventional tests that use AU-NP often have to amplify AU-NP's optical density, so that scientists can easily measure the strength of the signal produced by the interaction between antibodies and the target substance.

Adding more gold nanoparticles is one means to do this. But because nanoparticles are tiny, it requires a large quantity of them to achieve a strong enough signal for accurate detection.

To overcome this, the researchers proposed a new method called self-organized precipitation (SORP). SORP works by dissolving polymers into organic solvents before adding a liquid that doesn't dissolve the polymers well, like water. After the original organic solvent is removed by evaporation, polymers assemble together, forming tiny particles.

"Using gold nanoparticle decorated polymers (GDNP) assembled by SORP, we set out to see how effective they would be in detecting the influenza virus, and whether they offered improved sensitivity in detecting antigen-antibody reactions," states Hiroshi Yabu, co-author of the paper and professor at Tohoku University's Advanced Institute for Materials Research (AIMR). "And it did. Our method resulted in a higher optical density than original AU-NPs and GNDPs decorated with smaller AU-NPs."

Yabu and his colleagues' findings reinforce that GNDP particles have broad utility, extending beyond laboratory settings to real-world diagnostic scenarios.

About the World Premier International Research Center Initiative (WPI)

The WPI program was launched in 2007 by Japan's Ministry of Education, Culture, Sports, Science and Technology (MEXT) to foster globally visible research centers boasting the highest standards and outstanding research environments. Numbering more than a dozen and operating at institutions throughout the country, these centers are given a high degree of autonomy, allowing them to engage in innovative modes of management and research. The program is administered by the Japan Society for the Promotion of Science (JSPS).

See the latest research news from the centers at the WPI News Portal: https://www.eurekalert.org/newsportal/WPI
Main WPI program site:  www.jsps.go.jp/english/e-toplevel

Advanced Institute for Materials Research (AIMR), Tohoku University

Establish a World-Leading Research Center for Materials Science:

AIMR aims to contribute to society through its actions as a world-leading research center for materials science and push the boundaries of research frontiers. To this end, the institute gathers excellent researchers in the fields of physics, chemistry, materials science, engineering, and mathematics and provides a world-class research environment.

AIMR site: https://www.wpi-aimr.tohoku.ac.jp/en/
 

An immunoassay system that uses GNDP particles with antibodies

.  

A scan electron micrograph of GNDP particles. 

CREDIT

Hiroshi Yabu

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JOURNAL

Langmuir

DOI

10.1021/acs.langmuir.3c03890 

ARTICLE TITLE

Gold Nanoparticle-Decorated Polymer (GNDP) Particles for High-Optical-Density Immunoassay Probes

The Forgotten History of Hitler’s Establishment Enablers

By Adam GopnikApril 3, 2024Z ArticleNo Comments23 Mins Read
Source: The New Yorker
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GOEBELS CENTRE OF PHOTO LOOKS ALOT LIKE TRUMPS BRAIN; 

STEPHEN MILLER


Hitler is so fully imagined a subject—so obsessively present on our televisions and in our bookstores—that to reimagine him seems pointless. As with the Hollywood fascination with Charles Manson, speculative curiosity gives retrospective glamour to evil. Hitler created a world in which women were transported with their children for days in closed train cars and then had to watch those children die alongside them, naked, gasping for breath in a gas chamber. To ask whether the man responsible for this was motivated by reading Oswald Spengler or merely by meeting him seems to attribute too much complexity of purpose to him, not to mention posthumous dignity. Yet allowing the specifics of his ascent to be clouded by disdain is not much better than allowing his memory to be ennobled by mystery.

So the historian Timothy W. Ryback’s choice to make his new book, “Takeover: Hitler’s Final Rise to Power” (Knopf), an aggressively specific chronicle of a single year, 1932, seems a wise, even an inspired one. Ryback details, week by week, day by day, and sometimes hour by hour, how a country with a functional, if flawed, democratic machinery handed absolute power over to someone who could never claim a majority in an actual election and whom the entire conservative political class regarded as a chaotic clown with a violent following. Ryback shows how major players thought they could find some ulterior advantage in managing him. Each was sure that, after the passing of a brief storm cloud, so obviously overloaded that it had to expend itself, they would emerge in possession of power. The corporate bosses thought that, if you looked past the strutting and the performative antisemitism, you had someone who would protect your money. Communist ideologues thought that, if you peered deeply enough into the strutting and the performative antisemitism, you could spy the pattern of a popular revolution. The decent right thought that he was too obviously deranged to remain in power long, and the decent left, tempered by earlier fights against different enemies, thought that, if they forcibly stuck to the rule of law, then the law would somehow by itself entrap a lawless leader. In a now familiar paradox, the rational forces stuck to magical thinking, while the irrational ones were more logical, parsing the brute equations of power. And so the storm never passed. In a way, it still has not.

Ryback’s story begins soon after Hitler’s very incomplete victory in the Weimar Republic’s parliamentary elections of July, 1932. Hitler’s party, the National Socialist German Workers’ Party (its German initials were N.S.D.A.P.), emerged with thirty-seven per cent of the vote, and two hundred and thirty out of six hundred and eight seats in the Reichstag, the German parliament—substantially ahead of any of its rivals. In the normal course of events, this would have led the aging warrior Paul von Hindenburg, Germany’s President, to appoint Hitler Chancellor. The equivalent of Prime Minister in other parliamentary systems, the Chancellor was meant to answer to his party, to the Reichstag, and to the President, who appointed him and who could remove him. Yet both Hindenburg and the sitting Chancellor, Franz von Papen, had been firm never-Hitler men, and naïvely entreated Hitler to recognize his own unsuitability for the role.

The N.S.D.A.P. had been in existence since right after the Great War, as one of many völkisch, or populist, groups; its label, by including “national” and “socialist,” was intended to appeal to both right-wing nationalists and left-wing socialists, who were thought to share a common enemy: the élite class of Jewish bankers who, they said, manipulated Germany behind the scenes and had been responsible for the German surrender. The Nazis, as they were called—a put-down made into a popular label, like “Impressionists”—began as one of many fringe and populist antisemitic groups in Germany, including the Thule Society, which was filled with bizarre pre-QAnon conspiracy adepts. Hitler, an Austrian corporal with a toothbrush mustache (when Charlie Chaplin first saw him in newsreels, he assumed Hitler was aping his Little Tramp character), had seized control of the Party in 1921. Then a failed attempt at a putsch in Munich, in 1923, left him in prison, but with many comforts, much respect, and paper and time with which to write his memoir, “Mein Kampf.” He reëmerged as the leader of all the nationalists fighting for election, with an accompanying paramilitary organization, the Sturmabteilung (S.A.), under the direction of the more or less openly homosexual Ernst Röhm, and a press office, under the direction of Joseph Goebbels. (In the American style, the press office recognized the political significance of the era’s new technology and social media, exploiting sound recordings, newsreels, and radio, and even having Hitler campaign by airplane.) Hitler’s plans were deliberately ambiguous, but his purposes were not. Ever since his unsuccessful putsch in Munich, he had, Ryback writes, “been driven by a single ambition: to destroy the political system that he held responsible for the myriad ills plaguing the German people.”

Ryback skips past the underlying mechanics of the July, 1932, election on the way to his real subject—Hitler’s manipulation of the conservative politicians and tycoons who thought that they were manipulating him—but there’s a notable academic literature on what actually happened when Germans voted that summer. The political scientists and historians who study it tell us that the election was a “normal” one, in the sense that the behavior of groups and subgroups proceeded in the usual way, responding more to the perception of political interests than to some convulsions of apocalyptic feeling.

The popular picture of the decline of the Weimar Republic—in which hyperinflation produced mass unemployment, which produced an unstoppable wave of fascism—is far from the truth. The hyperinflation had ended in 1923, and the period right afterward, in the mid-twenties, was, in Germany as elsewhere, golden. The financial crash of 1929 certainly energized the parties of the far left and the far right. Still, the results of the July, 1932, election weren’t obviously catastrophic. The Nazis came out as the largest single party, but both Hitler and Goebbels were bitterly disappointed by their standing. The unemployed actually opposed Hitler and voted en masse for the parties of the left. Hitler won the support of self-employed people, who were in decent economic shape but felt that their lives and livelihoods were threatened; of rural Protestant voters; and of domestic workers (still a sizable group), perhaps because they felt unsafe outside a rigid hierarchy. What was once called the petite bourgeoisie, then, was key to his support—not people feeling the brunt of economic precarity but people feeling the possibility of it. Having nothing to fear but fear itself is having something significant to fear.

It was indeed a “normal” election in that respect, responding not least to the outburst of “normal” politics with which Hitler had littered his program: he had, in the months beforehand, damped down his usual ranting about Jews and bankers and moneyed élites and the rest. He had recorded a widely distributed phonograph album (the era’s equivalent of a podcast) designed to make him seem, well, Chancellor-ish. He emphasized agricultural support and a return to better times, aiming, as Ryback writes, “to bridge divides of class and conscience, socialism and nationalism.” By the strange alchemy of demagoguery, a brief visit to the surface of sanity annulled years and years of crazy.

The Germans were voting, in the absent-minded way of democratic voters everywhere, for easy reassurances, for stability, with classes siding against their historical enemies. They weren’t wild-eyed nationalists voting for a millennial authoritarian regime that would rule forever and restore Germany to glory, and, certainly, they weren’t voting for an apocalyptic nightmare that would leave tens of millions of people dead and the cities of Germany destroyed. They were voting for specific programs that they thought would benefit them, and for a year’s insurance against the people they feared.

Ryback spends most of his time with two pillars of respectable conservative Germany, General Kurt von Schleicher and the right-wing media magnate Alfred Hugenberg. Utterly contemptuous of Hitler as a lazy buffoon—he didn’t wake up until eleven most mornings and spent much of his time watching and talking about movies—the two men still hated the Communists and even the center-left Social Democrats more than they did anyone on the right, and they spent most of 1932 and 1933 scheming to use Hitler as a stalking horse for their own ambitions.

Schleicher is perhaps first among Ryback’s too-clever-for-their-own-good villains, and the book presents a piercingly novelistic picture of him. Though in some ways a classic Prussian militarist, Schleicher, like so many of the German upper classes, was also a cultivated and cosmopolitan bon vivant, whom the well-connected journalist and diarist Bella Fromm called “a man of almost irresistible charm.” He was a character out of a Jean Renoir film, the regretful Junker caught in modern times. He had no illusions about Hitler (“What am I to do with that psychopath?” he said after hearing about his behavior), but, infinitely ambitious, he thought that Hitler’s call for strongman rule might awaken the German people to the need for a real strongman, i.e., Schleicher. Ryback tells us that Schleicher had a strategy he dubbed the Zähmungsprozess, or “taming process,” which was meant to sideline the radicals of the Nazi Party and bring the movement into mainstream politics. He publicly commended Hitler as a “modest, orderly man who only wants what is best” and who would follow the rule of law. He praised Hitler’s paramilitary troops, too, defending them against press reports of street violence. In fact, as Ryback explains, the game plan was to have the Brown Shirts crush the forces of the left—and then to have the regular German Army crush the Brown Shirts.

Schleicher imagined himself a master manipulator of men and causes. He liked to play with a menagerie of glass animal figurines on his desk, leaving the impression that lesser beings were mere toys to be handled. In June of 1932, he prevailed on Hindenburg to give the Chancellorship to Papen, a weak politician widely viewed as Schleicher’s puppet; Papen, in turn, installed Schleicher as minister of defense. Then they dissolved the Reichstag and held those July elections which, predictably, gave the Nazis a big boost.

Ryback spends many mordant pages tracking Schleicher’s whirling-dervish intrigues, as he tried to realize his fantasy of the Zähmungsprozess. Many of these involved schemes shared with the patriotic and staunchly anti-Nazi General Kurt von Hammerstein-Equord (familiar to viewers of “Babylon Berlin” as Major General Seegers). Hammerstein was one of the few German officers to fully grasp Hitler’s real nature. At a meeting with Hitler in the spring of 1932, Hammerstein told him bluntly, “Herr Hitler, if you achieve power legally, that would be fine with me. If the circumstances are different, I will use arms.” He later felt reassured when Hindenburg intimated that, if the Nazi paramilitary troops acted, he could order the Army to fire on them.

Yet Hammerstein remained impotent. At various moments, Schleicher, as the minister of defense, entertained what was in effect a plan for imposing martial law with himself in charge and Hammerstein at his side. In retrospect, it was the last hope of protecting the republic from Hitler—but after President Hindenburg rejected it, not out of democratic misgivings but out of suspicion of Schleicher’s purposes, Hammerstein, an essentially tragic figure, was unable to act alone. He suffered from a malady found among decent military men suddenly thrust into positions of political power: his scruples were at odds with his habits of deference to hierarchy. Generals became generals by learning to take orders before they learned how to give them. Hammerstein hated Hitler, but he waited for someone else of impeccable authority to give a clear direction before he would act. (He went on waiting right through the war, as part of the equally impotent military nexus that wanted Hitler dead but, until it was too late, lacked the will to kill him.)

The extra-parliamentary actions that were fleetingly contemplated in the months after the election—a war in the streets, or, more likely, a civil confrontation leading to a military coup—seemed horrific. The trouble, unknowable to the people of the time, is that, since what did happen is the worst thing that has ever happened, any alternative would have been less horrific. One wants to shout to Hammerstein and his cohorts, Go ahead, take over the government! Arrest Hitler and his henchmen, rule for a few years, and then try again. It won’t be as bad as what happens next. But, of course, they cannot hear us. They couldn’t have heard us then.

Ryback’s gift for detail joins with a nice feeling for the black comedy of the period. He makes much sport of the attempts by foreign journalists resident in Germany, particularly the New York Times’ Frederick T. Birchall, to normalize the Nazi ascent—with Birchall continually assuring his readers that Hitler, an out-of-his-depth simpleton, was not the threat he seemed to be, and that the other conservatives were far more potent in their political maneuvering. When Papen made a speech denying that Hitler’s paramilitary forces represented “the German nation,” Birchall wrote that the speech “contained dynamite enough to change completely the political situation in the Reich.” On another occasion, Birchall wrote that “the Hitlerites” were deluded to think they “hold the best cards”; there was every reason to think that “the big cards, the ones that will really decide the game,” were in the hands of people such as Papen, Hindenburg, and, “above all,” Schleicher.

Ryback, focussing on the self-entrapped German conservatives, generally avoids the question that seems most obvious to a contemporary reader: Why was a coalition between the moderate-left Social Democrats and the conservative but far from Nazified Catholic Centrists never even seriously attempted? Given that Hitler had repeatedly vowed to use the democratic process in order to destroy democracy, why did the people committed to democracy let him do it?

Many historians have jousted with this question, but perhaps the most piercing account remains an early one, written less than a decade after the war by the émigré German scholar Lewis Edinger, who had known the leaders of the Social Democrats well and consulted them directly—the ones who had survived, that is—for his study. His conclusion was that they simply “trusted that constitutional processes and the return of reason and fair play would assure the survival of the Weimar Republic and its chief supporters.” The Social Democratic leadership had become a gerontocracy, out of touch with the generational changes beneath them. The top Social Democratic leaders were, on average, two decades older than their Nazi counterparts.


Worse, the Social Democrats remained in the grip of a long struggle with Bismarckian nationalism, which, however oppressive it might have been, still operated with a broad idea of legitimacy and the rule of law. The institutional procedures of parliamentarianism had always seen the Social Democrats through—why would those procedures not continue to protect them? In a battle between demagoguery and democracy, surely democracy had the advantage. Edinger writes that Karl Kautsky, among the most eminent of the Party’s theorists, believed that after the election Hitler’s supporters would realize he was incapable of fulfilling his promises and drift away.

The Social Democrats may have been hobbled, too, by their commitment to team leadership—which meant that no single charismatic individual represented them. Proceduralists and institutionalists by temperament and training, they were, as Edinger demonstrates, unable to imagine the nature of their adversary. They acceded to Hitler’s ascent with the belief that by respecting the rules themselves they would encourage the other side to play by them as well. Even after Hitler consolidated his power, he was seen to have secured the Chancellorship by constitutional means. Edinger quotes Arnold Brecht, a fellow exiled statesman: “To rise against him on the first night would make the rebels the technical violators of the Constitution that they wanted to defend.”

Meanwhile, the centrist Catholics—whom Hitler shrewdly recognized as his most formidable potential adversaries—were handicapped in any desire to join with the Democratic Socialists by their fear of the Communists. Though the Communists had previously made various alliances of convenience with the Social Democrats, by 1932 they were tightly controlled by Stalin, who had ordered them to depict the Social Democrats as being as great a threat to the working class as Hitler.

And, when a rumor spread that Hitler had once spat out a Communion Host, it only made him more popular among Catholics, since it called attention to his Catholic upbringing. Indeed, most attempts to highlight Hitler’s personal depravities (including his possibly sexual relationship with his niece Geli, which was no secret in the press of the time; her apparent suicide, less than a year before the election, had been a tabloid scandal) made him more popular. In any case, Hitler was skilled at reassuring the Catholic center, promising to be “the strong protector of Christianity as the basis of our common moral order.”

Hitler’s hatred of parliamentary democracy, even more than his hatred of Jews, was central to his identity, Ryback emphasizes. Antisemitism was a regular feature of populist politics in the region: Hitler had learned much of it in his youth from the Vienna mayor Karl Lueger. But Lueger was a genuine populist democrat, who brought universal male suffrage to the city. Hitler’s originality lay elsewhere. “Unlike Hitler’s anti-Semitism, a toxic brew of pseudoscientific readings and malignant mentoring, Hitler’s hatred of the Weimar Republic was the result of personal observation of political processes,” Ryback writes. “He hated the haggling and compromise of coalition politics inherent in multiparty political systems.”

Second only to Schleicher in Ryback’s accounting of Hitler’s establishment enablers is the media magnate Alfred Hugenberg. The owner of the country’s leading film studio and of the national news service, which supplied some sixteen hundred newspapers, he was far from an admirer. He regarded Hitler as manic and unreliable but found him essential for the furtherance of their common program, and was in and out of political alliance with him during the crucial year.

Hugenberg had begun constructing his media empire in the late nineteen-teens, in response to what he saw as the bias against conservatives in much of the German press, and he shared Hitler’s hatred of democracy and of the Jews. But he thought of himself as a much more sophisticated player, and intended to use his control of modern media in pursuit of what he called a Katastrophenpolitik—a “catastrophe politics” of cultural warfare, in which the strategy, Ryback says, was to “flood the public space with inflammatory news stories, half-truths, rumors, and outright lies.” The aim was to polarize the public, and to crater anything like consensus. Hugenberg gave Hitler money as well as publicity, but Hugenberg had his own political ambitions (somewhat undermined by a personal aura described by his nickname, der Hamster) and his own party, and Hitler was furiously jealous of the spotlight. While giving Hitler support in his media—a support sometimes interrupted by impatience—Hugenberg urged him to act rationally and settle for Nazi positions in the cabinet if he could not have the Chancellorship.

What strengthened the Nazis throughout the conspiratorial maneuverings of the period was certainly not any great display of discipline. The Nazi movement was a chaotic mess of struggling in-groups who feared and despised one another. Hitler rightly mistrusted the loyalty even of his chief lieutenant, Gregor Strasser, who fell on the “socialist” side of the National Socialists label. The members of the S.A., the Storm Troopers, meanwhile, were loyal mainly to their own leader, Ernst Röhm, and embarrassed Hitler with their run of sexual scandals. The N.S.D.A.P. was a hive of internal antipathies that could resolve only in violence—a condition that would endure to the last weeks of the war, when, standing amid the ruins of Germany, Hitler was enraged to discover that Heinrich Himmler was trying to negotiate a separate peace with the Western Allies.

The strength of the Nazis lay, rather, in the curiously enclosed and benumbed character of their leader. Hitler was impossible to discourage, not because he ran an efficient machine but because he was immune to the normal human impediments to absolute power: shame, calculation, or even a desire to see a particular political program put in place. Hindenburg, knowing of Hitler’s genuinely courageous military service in the Great War, appealed in their meetings to his patriotism, his love of the Fatherland. But Hitler, an Austrian who did not receive German citizenship until shortly before the 1932 election, did not love the Fatherland. He ran on the hydrogen fuel of pure hatred. He did not want power in order to implement a program; he wanted power in order to realize his pain. A fascinating and once classified document, prepared for the precursor of the C.I.A., the O.S.S., by the psychoanalyst Walter Langer, used first-person accounts to gauge the scale of Hitler’s narcissism: “It may be of interest to note at this time that of all the titles that Hitler might have chosen for himself he is content with the simple one of ‘Fuehrer.’ To him this title is the greatest of them all. He has spent his life searching for a person worthy of the role but was unable to find one until he discovered himself.” Or, as the acute Hungarian American historian John Lukacs, who spent a lifetime studying Hitler’s psychology, observed, “His hatred for his opponents was both stronger and less abstract than was his love for his people. That was (and remains) a distinguishing mark of the mind of every extreme nationalist.”

In November of 1932, one more Reichstag election was held. Once again, it was a bitter disappointment to Hitler and Goebbels—“a disaster,” as Goebbels declared on Election Night. (An earlier Presidential election had also reaffirmed Hindenburg over the Hitler movement.) The Nazi wave that everyone had expected failed to materialize. The Nazis lost seats, and, once again, they could not crack fifty per cent. The Times explained that the Hitler movement had passed its high-water mark, and that “the country is getting tired of the Nazis.” Everywhere, Ryback says, the cartoonists and editorialists delighted in Hitler’s discomfiture. One cartoonist showed him presiding over a graveyard of swastikas. In December of 1932, having lost three elections in a row, Hitler seemed to be finished.

The subsequent maneuverings are as dispiriting to read about as they are exhausting to follow. Basically, Schleicher conspired to have Papen fired as Chancellor by Hindenburg and replaced by himself. He calculated that he could cleave Gregor Strasser and the more respectable elements of the Nazis from Hitler, form a coalition with them, and leave Hitler on the outside looking in. But Papen, a small man in everything except his taste for revenge, turned on Schleicher in a rage and went directly to Hitler, proposing, despite his earlier never-Hitler views, that they form their own coalition. Schleicher’s plan to spirit Strasser away from Hitler and break the Nazi Party in two then stumbled on the reality that the real base of the Party was fanatically loyal only to its leader—and Strasser, knowing this, refused to leave the Party, even as he conspired with Schleicher to undermine it.

Then, in mid-January, a small regional election in Lipperland took place. Though the results were again disappointing for Hitler and Goebbels—the National Socialist German Workers’ Party still hadn’t surmounted the fifty-per-cent mark—they managed to sell the election as a kind of triumph. At Party meetings, Hitler denounced Strasser. The idea, much beloved by Schleicher and his allies, of breaking a Strasser wing of the Party off from Hitler became obviously impossible.

Hindenburg, in his mid-eighties and growing weak, became fed up with Schleicher’s Machiavellian stratagems and dispensed with him as Chancellor. Papen, dismissed not long before, was received by the President. He promised that he could form a working majority in the Reichstag by simple means: Hindenburg should go ahead and appoint Hitler Chancellor. Hitler, he explained, had made significant “concessions,” and could be controlled. He would want only the Chancellorship, and not more seats in the cabinet. What could go wrong? “You mean to tell me I have the unpleasant task of appointing this Hitler as the next Chancellor?” Hindenburg reportedly asked. He did. The conservative strategists celebrated their victory. “So, we box Hitler in,” Hugenberg said confidently. Papen crowed, “Within two months, we will have pressed Hitler into a corner so tight that he’ll squeak!”

“The big joke on democracy is that it gives its mortal enemies the tools to its own destruction,” Goebbels said as the Nazis rose to power—one of those quotes that sound apocryphal but are not. The ultimate fates of Ryback’s players are varied, and instructive. Schleicher, the conservative who saw right through Hitler’s weakness—who had found a way to entrap him, and then use him against the left—was killed by the S.A. during the Night of the Long Knives, in 1934, when Hitler consolidated his hold over his own movement by murdering his less loyal lieutenants. Strasser and Röhm were murdered then, too. Hitler and Goebbels, of course, died by their own hands in defeat, having left tens of millions of Europeans dead and their country in ruins. But Hugenberg, sidelined during the Third Reich, was exonerated by a denazification court in the years after the war. And Papen, who had ushered Hitler directly into power, was acquitted at Nuremberg; in the nineteen-fifties, he was awarded the highest honorary order of the Catholic Church.

Does history have patterns or merely circumstances and unique contingencies? Certainly, the Germany of 1932 was a place unto itself. The truth, that some cycles may recur but inexactly, is best captured in that fine aphorism “History does not repeat itself, but it sometimes rhymes.” Appropriately, no historian is exactly sure who said this: widely credited to Mark Twain, it was more likely first said long after his death.

We see through a glass darkly, as patterns of authoritarian ambition seem to flash before our eyes: the demagogue made strong not by conviction but by being numb to normal human encouragements and admonitions; the aging center left; the media lords who want something like what the demagogue wants but in the end are controlled by him; the political maneuverers who think they can outwit the demagogue; the resistance and sudden surrender. Democracy doesn’t die in darkness. It dies in bright midafternoon light, where politicians fall back on familiarities and make faint offers to authoritarians and say a firm and final no—and then wake up a few days later and say, Well, maybe this time, it might all work out, and look at the other side! Precise circumstances never repeat, yet shapes and patterns so often recur. In history, it’s true, the same thing never happens twice. But the same things do.